Next Article in Journal
Thermal Shock Resistance of Commercial Oxide-Bonded Silicon Carbide Reticulated Foams under Concentrated Solar Radiation at PSA: A Feasibility Study
Previous Article in Journal
ZnO and ZnO/Ce Powders as Tribocatalysts for Removal of Tetracycline Antibiotic
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Inorganics
Volume 12
Issue 9
10.3390/inorganics12090245
inorganics-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

The Structural Aspects of Mutually Trans-X-Cu(I)-X (X = OL, NL, CL, PL, SL, SeL, Cl or Br) Complexes

by
Milan Melník
1,*,
Veronika Mikušová
2 and
Peter Mikuš
1,3,*
1
Department of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, 832 32 Bratislava, Slovakia
2
Department of Galenic Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, 832 32 Bratislava, Slovakia
3
Toxicological and Antidoping Centre, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, 832 32 Bratislava, Slovakia
*
Authors to whom correspondence should be addressed.
Inorganics 2024, 12(9), 245; https://doi.org/10.3390/inorganics12090245
Submission received: 26 July 2024 / Revised: 28 August 2024 / Accepted: 4 September 2024 / Published: 6 September 2024
(This article belongs to the Section Coordination Chemistry)
Browse Figures
Versions Notes

Abstract

:
The structural parameters for sixty mutually trans-(X-Cu(I)-X) (X = OL, NL, CL, PL, SL, SeL, Cl or Br, where OL, NL, CL, PL, SL, and SeL are ligands L with respective donor atoms O, N, C, P, S and Se) complexes were analyzed and classified. Within the studied group, there are two types of complexes; the by far most common one is based on coordination, and another one is organometalics based on only C-donor atoms. Linear and bent geometric possibilities exist for coordination number two. The former is dominant in the structures of mutually trans -X–Cu(I)-X. In general, there are three preparative procedures; the most common is the direct reaction of a copper(I) salt with the ligands in a non-aqueous solution (mostly acetonitrile). Copper(I) complex cations can be isolated from salts with larger anions. Unidentate ligands occupy two coordination sites, which results in the linear arrangement. The X–Cu(I)–X angles are between 172.3° and 180°. Overall, it is observed that the mean Cu–X distance increases the covalent radius of the ligating atom in the sequence 1.849 Å (O, 0.73 Å) < 1.886 Å (N, 0.75 Å) < 1.900 Å (C, 0.77 Å) < 2.104 Å (Cl, 0.99 Å) < 2.137 Å (S, 1.02 Å) < 2.236 Å (P, 1.06 Å) < 2.244 Å (Br, 1.14 Å) < 2.260 Å (Se, 1.17 Å).

Graphical Abstract

1. Introduction

Although copper is in the oxidation state +2, the by far most common other known oxidation states include +1, +3 and +4, and, of these, Cu(I) is most common. Many structural studies of Cu(I) complexes have been carried out and have been sporadically summarized in annual reports [1,2,3]. The structural chemistry of simple halo(amine)Cu(I) compounds have also been reviewed [4].
The chemistry of copper compounds is an extensive and active area of study, with the relationships between structure, reactivity, and catalytic activity being of major importance. It is known that copper(I) is an effectively available monovalent ion for bonding variable organic molecules and halogens because of its high electron affinity. The most common for copper is, perhaps, electron transfer, which is especially associated with oxidative enzymes and energy capture [5,6,7]. The vast majority of X-ray studies on transition metal compounds focus on copper compounds. The copper in oxidation state +1 is prone to air oxidation and is unstable in an aqueous solution. Numerous stable copper(I) compounds have been synthesized using ligands with soft P-acid characteristics, while others exhibit relative stability due to their very low solubility. A comprehensive overview of copper structural chemistry has been studied, providing a survey length that ranges up to 1992 [8].
Two monodentate ligands build up mutually trans-(X-Cu(I)-X) type linear or X-Cu(I)-Y type bent complexes. This study aims to analyze structural data of over sixty mutually trans-(X-Cu(I)-X) complexes where X = OL, NL, CL, PL, SL, SeL, Cl, or Br.

2. Structural Aspects of Mutually Trans (X-Cu(I)-X) Complexes

There are eight types of such complexes, namely X-Cu(I)-X (X = OL, NL, CL, PL, SL, SeL, Cl or Br).

2.1. Homo -X-Cu(I)-X (X = OL, NL) Type

There are two complexes, monoclinic (NEt4)1+[Cu(η3-C44H62N2O8)]1− 0.5 (C2H13N) (at 188K) [9] and triclinic [Cu(C22H28N2)2]1+ [Cu(C10H9O2)2]1− (at 150K) [10], which are examples of the O-Cu(I)-O type. The monoderivative compounds of two crystallographically independent clusters differ solely in the orientation of the peripheral propyl groups. Each contains a linear two-coordinated copper(I) ligated by cis-carboxylate oxygen atoms. The structure of [Cu(η2-C44H62N2O8)]1− [9] is shown in Figure 1. The mean value of the Cu-O bond distance is 1.853(2) Å and the value of the O-Cu-O bond angle is 176.2(3)°.
The structure of the triclinic derivative consists of well-separated [Cu(C22H28N2)2]1+ and [Cu(C10H9O2)2]1−. The Cu(I) atom in the complex cation is twice coordinated via C-donor atoms of respective monodentate ligands (C-Cu(I)-C). The mean value of Cu-C bond distance is 1.913(2) Å and the C-Cu(I)-C bond angle is 176.5(2)°. The Cu(I) atom in a complex anion is coordinated by two monodentate ligands via O-donor atoms (O-Cu(I)-O). The mean value of the Cu-O bond distance is 1.842(3) Å and the O-Cu(I)-O bond angle is 176.3(2)°.
In three complexes—monoclinic [Cu(C5H8N2)2]ClO4 (at 100 K) [11], monoclinic [Cu(C30H42N4)2] BPh4 0.5(C6H6) 0.5 (CH2Cl2) (at 213 K) [12] and orthorhombic [Cu(C25H18N2)2] PF6 CH2Cl2 (at 193 K) [13]—a pair of monodentate ligands forms almost linear two-coordinate Cu(I) atoms (N-Cu(I)-N) via an N-donor atom. The mean value of the Cu-N bond distance is 1.878(3) Å and the mean value of the N-Cu(I)-N bond angle is 175.0(2)°.
The structure of triclinic [Cu(η2-C36H45N3P2Si2)]1+ [CuCl2]1− (at 100 K) [14] is shown in Figure 2. Homobidentate ligand creates a two-coordinate Cu(I) atom of N-Cu(I)-N-type via an N-donor. The mean value of the Cu-N bond distance is 1.852(2) Å and the mean value of the N-Cu(I)-N bond angle is 170.4(2)°. In [CuCl2], the chlorine linearly coordinates (Cl-Cu(I)-Cl). The mean value of the Cu-Cl bond distance is 2.106(4) Å and the mean value of the Cl-Cu-Cl bond angle is 176.4(3)°.
The structure of monoclinic [Cu(C13H25N3)2]1+ 2[Cu(C13H25N3)(Cl)]°[CuCl2] (at 133 K) [15] consists of well-separated complex units. In complex cation, two monodentate ligands form a linear N-Cu(I)-N-type via the N-donor atom, with a mean Cu-N bond distance of 1.865(2) Å. In [Cu(C13H25N3)(Cl)]°, the Cu(I) atom is two-coordinated by N-atom and chloro N-Cu(I)-Cl with the Cu-N and Cu-Cl bond distances of 1.884(3) Å and 2.090(2) Å. In [CCl2]1− the chlorine linearly coordinates Cl-Cu(I)-Cl and Cu-Cl distance is 2.103(4) Å.
The structure of the orthorhombic derivative consists of well-separated [Cu(C5H6N2)2]Cl and [Cu(C5H6N2)2Cl] (at 170 K) [16]. While, in the former, two monodentate ligands via N-donor atoms build up a linear type of the structure (N-Cu(I)-N), where the Cu-N bond distance is 1.885(2) Å and N-Cu(I)-N bond angle is 174.5(3)°, in the latter, i.e., [Cu(C5H6N2)2Cl], the Cu(I) is three coordinated (CuN2Cl) with the Cu-L bond distance of 1.928(3) Å (L = N1), 1.925(3) Å (L = N2) and 2.479(2) Å (L = Cl). The L-Cu-L bond angles open in the sequences 103.8(5)° (N1-Cu-Cl) < 105.2(3)° (N2-Cu-Cl) < 150.1(2)° (N1-Cu-N2). The data show that, in this complex, angular distortion from regular trigonal geometry occurs.
The structures of tetragonal [Cu(1-Mepz)2]BF4 and triclinic [Cu(1,3,5-Me3pz)2]BF4 are similar. The ligands via N-donor atoms create a linear N-Cu(I)-N type of structure. The mean value of Cu-N distances is 1.874 (4.7) Å and the mean value of N-Cu-N bond angles is 176.0 (1.2)° [17].

2.2. Homo -C-Cu(I)-C- Type

For such a type, there are 25 examples. These complexes crystalize in three crystal classes: tetragonal (one example) Cu(C33H40N2)2](I) (at 100 K) [18]; triclinic (six examples) [Cu(C12H28N2)2]1+ [Cu(C10H9O2)2]1− (at 150 K) [10] [Cu(C27H36N2)2]1+ (C6F18P)1− (at 100 K) [19]; [K(C12H24O6)(C4H8O)2]1+ [Cu(C≡CPh)2]1− (at 100 K) [20]; [Cu(C24H28N2O2)(C6F5)] (at 150 K) [21]; [Cu(C27H36N2)(C14H20N2O)] PF6 [22]; [Cu(C27H36N2)(C8H5)] 2 (C7H8) (at 100 K) [23], and monoclinic (18 examples): [Cu(C22H29N2) (C9H11)] 0.5 (C6H6) (at 150 K) [10], [Cu(C22H29N2) (C22H28N2)] (at 150 K) [10], [Cu(C22H29N2) (at 150 K) [10], [Cu(C33H40N2) (C27H36N2)] (I) (at 100 K) [18], [Cu(C27H35N2) (C7H13N2)] (C6F18P) (at 100 K) [19], [Cu(C7H12N2) (C6H5)] (at 100 K) [23], [Cu(C20H24N2) (C9H11)] (at 150 K) [24], [Cu(C23H30N2) (C9H11)] (at 150 K) [24], [Cu(C28H40N2) (C9H11) (at 150 K) [24], [Cu(C22H29N2) (C14H11) (at 150 K) [24], [Cu(C22H35N)2] (P≡CO) (at 100 K) [25], [Cu(C27H33N2) (C20H27Si) 0.5 (C6H14) (at 100 K) [26], [Cu(C27H33N2) (C26H38BF3N2O3Si)] 0.5 (C6H14)] (at 100 K) [26], [Cu(C21H28N2) (C18H15F3NSi)] (at 100 K) [26], [Cu(C27H33N2) (C10H14F4Si)] (at 123 K) [27], [Cu(C22H33N)2] PF6 CH2Cl2 [28], [Cu(C27H36N2)2] (C24H20B) 1.5 (C4H8O) (at 100 K) [29] and [Cu(C27H36N2)2] (C10H20BO4) (at 100 K) [30].
The structure of [Cu(C28H40N2) (C9H11) (at 150 K) [24] is shown in Figure 3 as an example. Monodentate C donor ligands create a C-Cu-C type. There are two groups of type one, in which both C-donor ligands are equal (C-Cu-C) and the other one is dissimilar (C-Cu-C′). In the former, the mean value of the Cu-C bond distances is 1.900 Å (range 1.822–1.943 Å) and the mean value of the C-Cu-C bond angles is 179.6° (range 178.1–180.0°). The respective values in the C-Cu-C′ type are 1.904 (range 1.870–1.925 Å) for Cu-C and 1.922 (range 1.893–1.942 Å) for Cu-C′. The mean value of C-Cu-C′ bond angles is 176.2 (range 172.9–177.9°). The same of Cu-C(x2) vs Cu-C′(x2) bond distances are 3.60 Å vs. 3.83 Å. The mean values of C-Cu-C vs C-Cu-C′ bond angles are 179.6 (range 178.1–180.0°) vs 176.2 (172.9–177.9°).

2.3. Homo -X-Cu(I)-X- (X = PL, SL, SeL) Types

In monoclinic [Cu(C33H60N9P)2] (CF3SO3) (at 100 K) [31], two monodentate P-donor ligands form a P-Cu-P type with two equal Cu-P bond distances of 2.236(2) Å. The P-Cu-P angle deviates by 7.7° from the linearity. This is the only example of such a type.
A triclinic [(C24H20P)]1+ [Cu(C3H9SiS)2]1−, at (100 K) [32] is the only example of the -S-Cu-S-type. The structure of [Cu(C3H9SiS)2]1− [32] is shown in Figure 4. Two equal monodentate S-donor ligands build up an almost linear S-Cu-S type with a S-Cu-S bond angle of 178.6(2)° and a Cu-S bond distance of 2.137(5) Å (x2).
There are three complexes, triclinic [(C36H30NP2)]1+ [Cu(C3H9SiSe)2]1− at 100) [32], and two monoclinic [Cu(C21H24N2Se)2] PF6 (at 298 K) [33], and [Cu(C27H36N2Se)2] PF6 (at 298 K) [33] in which a pair of monodentate Se-donor ligands create a linear Se-Cu-Se type (180.0°). The mean values of the Cu-Se bond distances are 2.260 (range 2.253–2.267 Å).

2.4. Homo -X-Cu(I)-X- (X = Cl, Br) Types

There are thirteen complexes which consist of variable complexes of organic cation and well-separated [CuCl2]1−. Such complexes are triclinic [Cu(η2C36H45N3P2Si2)]1+ [CuCl2]1− [14], monoclinic [Cu(C13H25N3)2]21+ [Cu(C13H25N3) (Cl)]° [CuCl2] [15], monoclinic [Cu(η4-C24H36N6S2)]1+ [CuCl2]1− [34], monoclinic [Cu2(η4-C26H40N6S4) (η-Cl)]1+ [CuCl2]1− (at 130 K) [35], monoclinic [C22H28N6]1+ [CuCl2]1− (at 120 K) [36], monoclinic [C13H20N5S]1+ [CuCl2]1− (at 100 K) [36], monoclinic [C13H26N3]1+ [CuCl2]1− (at 123 K) [37], monoclinic [C10H14NS]1+ [CuCl2]1− (at 150 K) [38], monoclinic [C25H22P]1+ [CuCl2]1− (at 133 K) [39], monoclinic [5(C4H12N1+)] [InCl63−] [CuCl2] (Cl) (at 300 K) [40], triclinic [C48H90N12Si2]2+2 [CuCl2]1− (at 120 K) [41], and monoclinic [(C15H32N3)1+ [CuCl2]1− (at 150 K) [42].
The total mean value of the Cu-Cl bond distance is 2.105 (range 2.087–2.120 Å). The total mean value of the Cl-Cu-Cl bond angles is 176.2 (range 173.9–180.0°).
There are six Cu(I) complexes in which a pair of Br anions form an almost linear [Br-Cu(I)-Br] type. Such complexes are monoclinic [Cu(η4-C24H36N6S2)]1+ [CuBr2]1− (at 130 K) [34], monoclinic [C15H32N3]1+ [CuBr2]1− (at 150 K) [42], triclinic [C38H28O8S8]1+ [CuBr2]1− (CH3CN) (at 293 K) [43], triclinic [C42H36O8S8]1+ [CuBr2]1− (at 293 K) [43], monoclinic [C16H36N1]1+ [CuBr2]1− (at 293 K) [44], and triclinic [Cu(II)(η4-C21H48N10)(Cl)]1+ [CuBr2]1− (at 120 K) [45]. The mean Cu-Br bond distance is 2.244 (range 2.216–2.284 Å) and the mean Br-Cu-Br bond angle is 177.6 (range 175.4–180.0°).

3. Conclusions

This structural study has analyzed sixty mutually trans -X-Cu(I)-X (X = OL, NL, CL, PL, SL, Se L, Cl, or Br) complexes which have been prepared by three basic synthetic methods. The most common is the direct reaction of a copper(I) salt with the ligands in a non-aqueous solution (mostly acetonitrile). In the second method, copper(II) salts are reduced in the presence of reducing ligands, mostly of the S, Se, or P donor type. In the third method, ascorbic acid is used as the reducing agent. Copper(I) complex cations can be isolated from salts with larger anions, both organic and inorganic (for example, ClO4, PF6, PPh4, CF3SO3, and others).
Copper(I) complexes are mostly colorless, but there are many colored examples too, and they are caused either by ligand absorption or charge-transfer bands.
The total mean values of Cu-L, X-Cu-X and the covalent radius of X are listed in Table 1.
The two coordination sites are occupied by unidentate ligands, which permits the linear arrangement to be adapted. The data in Table 1 show X-Cu-X angles between 172.6°and 180.0°. The mean Cu-X distance increases with the increasing covalent radius of the ligating atom (Table 1).
In summary, this is the first part of our structural analysis of Cu(I) complexes. In twice coordinated Cu(I) complexes, two monodentate ligands build up a mutually trans-(X-Cu(I)-X) type linear or X-Cu(I)-Y type bent complexes, and, here, we analyzed the structural data of mutually trans-(X-Cu(I)-X) complexes with variable monodentate ligands and donor atoms. Thus, in our subsequent study, a structural analysis of X-Cu(I)-Y will be carried out to complete the twice-coordinated compounds of Cu(I). Prospectively, we will then continue with Cu(I) and its coordination no. 3, 4, etc. to obtain a detailed insight into a whole group of Cu(I) complexes and their structural parameters.

Author Contributions

Conceptualization, M.M. and P.M.; Methodology M.M. and P.M.; Writing—Original Draft Preparation, M.M. and P.M.; Data Curation, M.M.; Writing—Review and Editing, V.M.; Supervision, M.M. and P.M.; Funding Acquisition, P.M. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the project VEGA 1/0514/22, VEGA 1/0146/23.

Data Availability Statement

All data generated or analyzed during this study are included in this published article.

Acknowledgments

This work was supported by the Faculty of Pharmacy, Comenius University, Bratislava. Structural data were used in this study for discussion, and calculations were obtained from Cambridge Crystallographic Database (CCDB) with an institutional license of the Slovak University of Technology in Bratislava.

Conflicts of Interest

The authors declare no conflicts of interest.

Abbreviations

BPh41−tetraphenylborate
C2H3Nacetonitrile
C3H9SiStrimethylsitanethotate
C3H9SiSetrimethylsilaneselenotate
C4H12Nn-butylammonium
C4H8Otetrahydrofuran
C5H6N2pyridine-4-amine
C5H8N43,5-dimethyl-1H-pyrazole
C6F18Ptrifluoro(tris(pentafluoroethyl)phosphate
C6F18P1trifluoro[bis(pentafluoroethyl)phosphate
C6F5pentafluorophenyl
C6H14hexane
C6H5phenyl
C7H12N21,3,4,5-tetramethylimidazol-2-ylidene
C7H13N2(1,3,4,5-tetramethylimidazol-2-ylidene)
C8H5phenylethynyl
C9H11mesityl
C9H9(1-phenylprop-1-en-1-yl)
C10H12ClN4bis(pyridine-4-amine)
C10H14F4Si((2-dimethyl(phenyl)sibyl)1,1,2,2-tetrafluoro-ethyl)
C10H14NS3,3-dimethyl-3,4-dihydro-2H-1,3-benzothiazim-ium
C10H20BO4bis(2,2-dimethylpropane-1,3-diolate)
C10H9O2(2-phenylbut-2-enoato)
C12H24O618-crown-6
C13H20N5S1-[bis(dimethylamino)methylidene]-2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)
C13H25N3(2,6-di-t-butyl-2,3,5,6-tetrahydro-1H-imidazo [1,2_a]-imidazole
C13H26N32,6-di-t-butyl-2,3,5,6-tetrahydro-1H-imidazol [1,2,a]imidazol-7-ium
C14H20N2O(1-(2-hydroxyethyl-3-(2,4,6-trimethylphenyl)imidazolidine-2-ylidene)
C15H32N31,3,5-tri-t-butyl-2,3,4,5-tetrahydro-1,3,5-triazin-1-ium
C16H36N1tetra-n-butylammonium
C18H15F3NSi(3-(3-cyanophenyl)-3-(dimethyl(phenyl)sibyl)-1,1,1-trifluoropropan-2-yl)
C20H24N2(1,3-bis(2,6-dimethylphenyl)hexahydro-pyrimidin-2-ylidne)
C20H27Si(4-((t-1-butyl(diphenyl)sibyl)oxy)-1,1,1-trifluorobutan-2-yl)
C21H24N2Se[1,3-bis(2,4,6-trimethylphenyl)-1.3-dihydro-2H-imidazole-2-selone]
C21H28N2(1,3-bis(2,4,6-trimethylphenyl)imidazolidine-2-ylidene)
C21H46N10Clchloro-(2,2′,2″-((nitrilo)truthane-2,1-diyl)tris(1,1,3,3-tetramethylquanidine)
C22H28N2(1,3-dimesityltetrahydropyrimidin-2(1H)-ylidene)
C22H28N62,2′-hydrazinediylildenebis(1,3-diethyl-2,3-dihydro-1H-benzimidazole)
C22H29N2(1,3-dimesitylhexahydropyrimidin-2-yl)
C22H29N2(1,3-dimesityltetrahydropyrimidin-2(1H)-ylidene)
C22H33N(2-(2,6-di-isopropylyphenyl)-1,4,5-trimethyl-2-azabicyclo(2,2,2)octan-3-ylidne)
C23H25N3(2,6-di-t-butyl—2,3,5,6-tetrahydro-1H-ionidazo(1,2-a)imidazole
C23H30N2(1,3-bis(2,4,6-trimethylphenyl)1,3-diazepan-2-ylidene)
C24H20Btetraphenylborate
C24H20P1+tetraphenylphosphonium
C24H28N2O2(1,3-dimesityl-5,5-dimethyl-4,6-diolotetrahydropyrimidin-2(1H)ylidene)
C24H36N6S2(N″,N′″-(ethane-1,2-diylbis(sulfanidiyl)2-phenylene))bis(N,N,N′,N′-tetramethyl-quanidine))
C25H18N2(1-isoquinolin-1-yl)-N-phenylnaphtalen-2-amine)
C25H22Pbenzyl(triphenyl)phosphonium
C26H38BF3N2O3Si(4-((t-butyl(diphenyl)sibyl)oxy)-1,1,1-trifluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-yl)
C26H40N6S4Cl(N-N″,N′″-(disulfanediylbis((ethane-2,1-diyl)sulfanediyl-2,1-phenylene))bis(N,N,N′,N′-tetramethylquanidine)-(u-chloro)
C27H33N2(1,3-bis(2,6-bis(propan-2-yl))phenyl]-2,3-dihydro-1H-imidazol-2-ylidene)
C27H36N2(1,3-bis(2,6-di-isopropylphenyl)-2,3-dihydro-1H-imidazol-2-ylidene)
C27H36N2(1,3-bis(2,6-disopropylphenyl)-imidazol-2-ylidene)
C27H36N21,3-bis[2,6-bis(propan-2-yl)phenyl]imidazole-2-ylidene)
C27H36N2Se[1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazole-2-selone]
C28H35N(1-(2,6-diisopropylphenyl)-3,3-dithyl-5)5-dimethylpyriolidin-2-ylidene)
C30H42N4(2-(N,N′-bis(2,6-diisopropylphenyl)carbamimidoyl)-1,3-dimethyl-1H-imidazol-3-iumato)
C33H40N21,3-bis[2,6-di-isopropylphenyl]-2-phenyl-1H-imidazol-3-ium-4-yl]
C33H60N9P(N,N′,N″-tris(1,3-disopropyl-4,5-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene)phosphorous triamide)
C36H45N3P2Si2(2,5-bis{[P,P-diphenyl-N-(trimethylsilyl)phosphorimidoyl)methyl)-1H-pyrrole)
C38H28N8S82-(4,5-bis((2-(methoxycarbonyl)phenyl)sulfanyl)-1,3-dithiol-2-ylidene)-4,5-bis((2-methoxycarbonyl)phenyl)sulfanyl-1,3-dithiol-1-ium
C42H36O8S82-(4,5-bis((4-ethoxycarbonyl)phenyl)sulfanyl)-1,3-dithiol-2-ylidene)-4,5-bis((4-(ethoxycarbonyl)phenyl)sulfanyl)-1,3-dithiol-1-ium
C44H62N2O8(4,6-dimethyl-1,3-bis(1,5,7-tripropyl-3-azabicyclo(3.3.1)none-2,4-dione-7-carboxylato)benzene)
C48H90N12Si22,2′,2″,2′″-(3,6-bis([tris(propan-2-yl)silyl]ethynyl)benzene-1,2,4,5 tetrayl)tetraphis (1,1,3,3-tetramethylquanidine)
Memethyl
Met42tetraethylammonium
P≡COphosphinedyne
pzpyrazole

References

  1. Hattaway, B.J. Copper. Coord. Chem. Rev. 1981, 35, 211–252. [Google Scholar] [CrossRef]
  2. Hattaway, B.J. Copper. Coord. Chem. Rev. 1982, 41, 423–487. [Google Scholar] [CrossRef]
  3. Hattaway, B.J. Copper. Coord. Chem. Rev. 1983, 52, 87–169. [Google Scholar] [CrossRef]
  4. O’Brien, P. Copper. Coord. Chem. Rev. 1984, 58, 169–244. [Google Scholar] [CrossRef]
  5. Sigel, H. (Ed.) Metal Ions in Biological Systems: Properties of Copper Volume 12, 1st ed.; Marcel Dekker Inc: New York, NY, USA, 1981; 400p. [Google Scholar]
  6. Sigel, H. Metal Ions in Biological Systems: Copper Proteins Volume 13, 1st ed.; Sigel, H., Sigel, A., Eds.; Marcel Dekker Inc: New York, NY, USA, 1982; 400p. [Google Scholar]
  7. Lontie, R. (Ed.) Copper Proteins and Copper Enzymes, Volume 1, 1st ed.; CRC Press: Boca Raton, FL, USA, 1984; 233p. [Google Scholar]
  8. Holloway, C.E.; Melník, M. Copper(I) Compounds: Classification and analysis of Crystallographic and structural Data. Rev. Inorg. Chem. 1995, 15, 147–386. [Google Scholar] [CrossRef]
  9. Le Cloux, D.D.; Lippard, S.J. Synthesis and Characterization of a Novel Class of Dicopper(I) Bis(carboxylate)-Bridged Complexes. Inorg. Chem. 1997, 36, 4035–4046. [Google Scholar] [CrossRef]
  10. Collins, L.R.; Riddlestone, I.M.; Mahon, M.F.; Whittlesey, M.K. A Comparison of the Stability and Reactivity of Diamido- and Diaminocarbene Copper Alkoxide and Hydride Complexes. Chem. Eur. J. 2015, 21, 14075–14084. [Google Scholar] [CrossRef] [PubMed]
  11. Luk’yanov, M.; Slyvka, Y.; Kinzhybalo, V.; Mys´kiv, M. Synthesis, crystal structure and Hirshfeld surface analysis of the [Cu2(3,5-dimethyl-1H-pyrazole)4(ClO4)2] complex. Chem. Met. Alloys 2016, 9, 27–33. [Google Scholar] [CrossRef]
  12. Marquez, A.; Avila, E.; Urbaneja, C.; Alvarez, E.; Palma, P.; Campora, J. Copper(I) Complexes of Zwitterionic Imidazolium-2-Amidinates, a Promising Class of Electroneutral, Amidinate-Type Ligands. Inorg. Chem. 2015, 54, 11007–11017. [Google Scholar] [CrossRef]
  13. Ramirez-Lopez, P.; Ros, A.; Romero-Arenas, A.; Iglesias-Siguenza, J.; Fernandez, R.; Lassaletta, J.M. Synthesis of IAN-type N,N-Ligands via Dynamic Kinetic Asymmetric Buchwald-Hartwig Amination. J. Am. Chem. Soc. 2016, 138, 12053–12056. [Google Scholar] [CrossRef]
  14. Jha, V.K.; Das, S.; Subramaniyan, V.; Guchhait, T.; Dakua, K.K.; Mishra, S.; Mani, G. Synthesis, structural characterization, and bonding analysis of two-coordinate copper(i) and silver(i) complexes of pyrrole-based bis(phosphinimine): New metal–pyrrole ring π-interactions. Dalton Trans. 2021, 50, 8036–8044. [Google Scholar] [CrossRef] [PubMed]
  15. Ge, Y.; Cui, X.Y.; Tan, S.M.; Jiang, H.; Ren, J.; Lee, N.; Lee, R.; Tan, C.H. Guanidine-Copper Complex Catalyzed Allylic Borylation for the Enantioconvergent Synthesis of Tertiary Cyclic Allylboronates. Angew. Chem. 2019, 58, 2382–2386. [Google Scholar] [CrossRef]
  16. Skelton, B.W. (Crystallography Centre and Department of Chemistry, University of Western Australia, Nedlands, WA 6907, Australia); Healy, P.C. (Faculty of Science and Technology, Griffith University, Nathan, Brisbane, QLD 4111, Australia). CSD Communication (2018) CBEWHOD, 2022. (Private communication).
  17. Sorrell, T.N.; Jameson, D.L. Synthesis, structure, and reactivity of monomeric two-coordinate copper(I) complexes. J. Am. Chem. Soc. 1983, 105, 6013–6018. [Google Scholar] [CrossRef]
  18. Ho, N.K.T.; Reichmann, S.O.; Rottschafer, D.; Herbst-Irmer, R.; Ghadwal, R.S. Expanding the Scope of Cu(I) Catalyzed “Click Chemistry” with Abnormal NHCs: Three-Fold Click to Tris-Triazoles. Catalysts 2017, 7, 262. [Google Scholar] [CrossRef]
  19. Fochrenbach, S.A.; Kuhfuss, M.J.; Zaff, L.; Friedroch, A.; Ignalev, N.V.; Finze, M.; Radius, U. Tris (pentafluoroethyl) difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry. Chem. A Eur. J. 2021, 27, 3504–3516. [Google Scholar] [CrossRef] [PubMed]
  20. Seifert, T.P.; Boukis, A.C.; Feuerstein, T.J.; Roesky, P.W. A straightforward synthetic route to symmetric bis(acetylide) metallates of the coinage metals. J. Organomet. Chem. 2018, 867, 92–97. [Google Scholar] [CrossRef]
  21. Shi, S.; Collins, L.R.; Mahon, M.F.; Djurovich, P.I.; Thompson, M.E.; Whittlesey, M.K. Synthesis and characterization of phosphorescent two-coordinate copper(i) complexes bearing diamidocarbene ligands. Dalton Trans. 2017, 46, 745–752. [Google Scholar] [CrossRef]
  22. Thiel, N.O.; Brechmann, L.T.; Teichert, J.F. Catalytic Hydrogenations with Cationic Heteroleptic Copper(I)/N-Heterocyclic Carbene Complexes. Synlett 2019, 30, 783–786. [Google Scholar] [CrossRef]
  23. Plotzitzka, J.; Kleeberg, C. [(NHC)CuI–ER3] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort CuI···CuI Distances. Inorg. Chem. 2016, 55, 4813–4823. [Google Scholar] [CrossRef]
  24. Hall, J.; Unson, D.; Brunel, P.; Collins, L.; Cybulski, M.; Mahon, M.; Whittlesey, M.K. Copper-NHC-Mediated Semi-Hydrogenation and Hydroboration of Alkynes: Enhanced Catalytic Activity Using Ring-Expanded Carbenes. Organometallics 2018, 37, 3102–3110. [Google Scholar] [CrossRef]
  25. Liu, L.L.; Ruiz, D.A.; Dahcheh, F.; Bertrand, G.; Suter, R.; Tondreau, A.M.; Grutzmacher, H. Isolation of Au-, Co-η1PCO and Cu-η2PCO complexes, conversion of an Ir–η1PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion. Chem. Sci. 2016, 7, 2335–2341. [Google Scholar] [CrossRef] [PubMed]
  26. Paioti, P.H.S.; del Pozo, J.; Mikus, M.S.; Lee, J.; Koh, M.J.; Romiti, F.; Torker, S.; Hoveyda, A.H. Catalytic Enantioselective Boryl and Silyl Substitution with Trifluoromethyl Alkenes: Scope, Utility, and Mechanistic Nuances of Cu–F β-Elimination. J. Am. Chem. Soc. 2019, 141, 19917–19934. [Google Scholar] [CrossRef] [PubMed]
  27. Sakaguchi, H.; Okashi, M.; Ogoshi, S. Fluorinated Vinylsilanes from the Copper-Catalyzed Defluorosilylation of Fluoroalkene Feedstocks. Angew. Chem. Int. Ed. Engl. 2018, 57, 328–332. [Google Scholar] [CrossRef] [PubMed]
  28. Manar, K.K.; Chakrabortty, S.; Porwal, V.K.; Prakash, D.; Thakur, S.K.; Choudhury, A.R.; Singh, S. Two-Coordinate Cu(I) and Au(I) Complexes Supported by BICAAC and CAAC Ligands. ChemistrySelect 2020, 5, 9900–9907. [Google Scholar] [CrossRef]
  29. Ritter, F.; Mukherjee, D.; Spaniol, T.P.; Hoffmann, A.; Okuda, J. A Masked Cuprous Hydride as a Catalyst for Carbonyl Hydrosilylation in Aqueous Solutions. Angew. Chem. Int. Ed. 2019, 58, 1818–1822. [Google Scholar] [CrossRef]
  30. Drescher, W.; Borner, C.; Kleeberg, C. Stability and decomposition of copper(i) boryl complexes: [(IDipp)Cu–Bneop], [(IDipp*)Cu–Bneop] and copper clusters. New J. Chem. 2021, 45, 14957–14964. [Google Scholar] [CrossRef]
  31. Mehlmann, P.; Muck-Lichtenfeld, C.; Tan, T.Y.T.; Dielmann, F. Tris(imidazolin-2-ylidenamino)phosphine: A Crystalline Phosphorus(III) Superbase That Splits Carbon Dioxide. Chem. A Eur. J. 2017, 23, 5929–5933. [Google Scholar] [CrossRef]
  32. Guschlbauer, J.; Vollgraff, T.; Xie, X.; Weigend, F.; Sundermeyer, J. A Series of Homoleptic Linear Trimethylsilylchalcogenido Cuprates, Argentates and Aurates Cat[Me3SiE–M–ESiMe3] (M = Cu, Ag, Au; E = S, Se). Inorg. Chem. 2020, 59, 17565–17572. [Google Scholar] [CrossRef]
  33. Srinivas, K.; Prabusankar, G. Role of C, S, Se and P donor ligands in copper(i) mediated C–N and C–Si bond formation reactions. RSC Adv. 2018, 8, 32269–32282. [Google Scholar] [CrossRef]
  34. Florke, U. (Department Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstraße 100, 33098 Paderborn, Germany); Nagel, C. (Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany); Henkel, G. CSD Communication (IVANKAR), 2017. (Private communication).
  35. Florke, U. (Department Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstraße 100, 33098 Paderborn, Germany); Bernard, M. (Institut Charles Sadron 6, rue Boussingault, F-67083 Strasbourg Cedex, France); Henkel, G. (Institut für Anorganische Chemie, Westfälische Wilhelms-Universität Münster, 4400 Münster, Germany). CSD Communication, ZAJBUK, 2017. (Private communication).
  36. Werr, M.; Kaifer, E.; Wadepohl, H.; Himmel, H.J. Tuneable Redox Chemistry and Electrochromism of Persistent Symmetric and Asymmetric Azine Radical Cations. Chem. A Eur. J. 2019, 25, 12981–12990. [Google Scholar] [CrossRef]
  37. Cui, X.Y.; Ge, Y.; Tan, S.M.; Jiang, H.; Tan, D.; Lu, Y.; Lee, R.; Tan, C.H. (Guanidine)copper Complex-Catalyzed Enantioselective Dynamic Kinetic Allylic Alkynylation under Biphasic Condition. J. Am. Chem. Soc. 2018, 140, 8448–8455. [Google Scholar] [CrossRef] [PubMed]
  38. Siegler, M.A. (Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA); Spek, A.L. (Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, Utrecht, The Netherlands); Sperotto, E. (Chemical Biology and Organic Chemistry, Utrecht University, Padualaan 8, 3584 CH, Utrecht, The Netherlands); Klein Gebbink, R.J.M. (Organic Chemistry and Catalysis, Debye Institute for NanoMaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands). CSD Communication BABRUV, 2015. (Private communication).
  39. Jones, P.G. (Fachbereich Chemie und Pharmazie, Technische Universität Braunschweig, Postfach 3329, 38023 Braunschweig, Germany); Daniliuc, C.G. (Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, Münster 48149, Germany); du Mont, W.W. (Fachbereich Chemie und Pharmazie, Technische Universität Braunschweig, Postfach 3329, 38023 Braunschweig, Germany). CSD Communication BUCJEF, 2015. (Private communication).
  40. Connor, B.A.; Smaha, R.W.; Li, J.; Gold-Parker, A.; Heyer, A.J.; Toney, M.F.; Lee, Y.S.; Karunadasa, H.I. Alloying a single and a double perovskite: A Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption. Chem. Sci. 2021, 12, 8689–8697. [Google Scholar] [CrossRef] [PubMed]
  41. Wagner, C.; Kreis, F.; Popp, D.; Hubner, O.; Kaifer, R.; Himmel, H.J. 1,2,4,5-Tetrakis(tetramethylguanidino)-3,6-diethynyl-benzenes: Fluorescent Probes, Redox-Active Ligands and Strong Organic Electron Donors. Chemistry 2020, 26, 10336–10347. [Google Scholar] [CrossRef]
  42. Khatua, S.; Majumdar, A. Cleavage of carbon–nitrogen bond in 1,3,5-tri-tert-butyl-1,3,5-triazacyclohexane by copper(I) bromide. J. Mol. Struct. 2016, 1120, 267–273. [Google Scholar] [CrossRef]
  43. Ma, L.; Sun, J.; Li, X.; Zhang, S.; Qi, H.; Liu, L.; Shao, Y.; Shao, X. Copper ion salts of arylthiotetrathiafulvalenes: Synthesis, structure diversity and magnetic properties. Beilstein J. Org. Chem. 2015, 11, 850. [Google Scholar] [CrossRef]
  44. Chen, S.; Gao, J.; Chang, J.; Li, Y.; Huangfu, C.; Meng, H.; Wang, Y.; Xia, G.; Fang, L. Family of Highly Luminescent Pure Ionic Copper(I) Bromide Based Hybrid Materials. ACS Appl. Mat. Interfaces 2019, 11, 17513–17520. [Google Scholar] [CrossRef]
  45. Florke, U. (Department Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstraße 100, 33098 Paderborn, Germany). CSD Communication OJIFIY, 2016. (Private communication).
Inorganics 12 00245 g001
Figure 1. Structure of [Cu{η3-C44H62N2O8}]1− [9].
Figure 1. Structure of [Cu{η3-C44H62N2O8}]1− [9].
Inorganics 12 00245 g001
Inorganics 12 00245 g002
Figure 2. Structure of [Cu(C36H45N3P2Si2)]1− [14].
Figure 2. Structure of [Cu(C36H45N3P2Si2)]1− [14].
Inorganics 12 00245 g002
Inorganics 12 00245 g003
Figure 3. Structure of [Cu(C28H40N2)(C9H11)] [24].
Figure 3. Structure of [Cu(C28H40N2)(C9H11)] [24].
Inorganics 12 00245 g003
Inorganics 12 00245 g004
Figure 4. Structure of [Cu(C3H9SiS)2]1− [32].
Figure 4. Structure of [Cu(C3H9SiS)2]1− [32].
Inorganics 12 00245 g004
Table 1. Total mean values of Cu-L, X-Cu-X, and the covalent radius of X.
Table 1. Total mean values of Cu-L, X-Cu-X, and the covalent radius of X.
X-Cu(I)-XCu-X [Å]X (cov. r.) [Å]X-Cu-X [°]
O-Cu(I)-O1.849O (0.73)176.5
N-Cu(I)-N1.886N (0.75)174.5
C-Cu(I)-C1.900C (0.77)174.0
Cl-Cu(I)-Cl2.104Cl (0.99)175.9
S-Cu(I)-S2.137S (1.02)178.6
P-Cu(I)-P2.236P (1.06)172.6
Br-Cu(I)-Br2.244Br (1.14)178.4
Se-Cu(I)-Se2.260Se (1.17)180.0
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Melník, M.; Mikušová, V.; Mikuš, P. The Structural Aspects of Mutually Trans-X-Cu(I)-X (X = OL, NL, CL, PL, SL, SeL, Cl or Br) Complexes. Inorganics 2024, 12, 245. https://doi.org/10.3390/inorganics12090245

AMA Style

Melník M, Mikušová V, Mikuš P. The Structural Aspects of Mutually Trans-X-Cu(I)-X (X = OL, NL, CL, PL, SL, SeL, Cl or Br) Complexes. Inorganics. 2024; 12(9):245. https://doi.org/10.3390/inorganics12090245

Chicago/Turabian Style

Melník, Milan, Veronika Mikušová, and Peter Mikuš. 2024. "The Structural Aspects of Mutually Trans-X-Cu(I)-X (X = OL, NL, CL, PL, SL, SeL, Cl or Br) Complexes" Inorganics 12, no. 9: 245. https://doi.org/10.3390/inorganics12090245

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop