Copper(I) Arenethiolates with Intramolecular Coordination and the Formation of Mixed Organo(arenethiolato)copper(I) Aggregates. X-ray Structures of Trimeric [Cu(SC6H4NMe2
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- 作者：Maurits D. Janssen ; Johannes G. Donkervoort ; Sofia B. van Berlekom ; Anthony L. Spek ; David M. Grove ; and Gerard van Koten
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：July 31, 1996
- 年：1996
- 卷：35
- 期：16
- 页码：4752 - 4763
- 全文大小：394K
- 年卷期：v.35,no.16(July 31, 1996)
- ISSN：1520-510X
文摘
Two new copper(I) arenethiolates withortho-chelating nitrogen donor atoms[Cu(SC6H4NMe2-2)]3(5) and [Cu(S-1-C10H6NMe2-8)]9(6) have been synthesized by reactingMe3SiSAr (Ar =C6H4NMe2-2 or1-C10H6NMe2-8)with copper(I) chloride in a 1:1 molar ratio. Copper(I)arenethiolate 5 is a white to pale yellow solid andistrimeric in the solid state as well as in solution. Crystals of[Cu(SC6H4NMe2-2)]3(5),C24H30Cu3N3S3,are trigonal,space group R3, with a = b =18.2325(7) Å, c = 6.8410(4) Å, V= 1969.4(2) Å3, Z = 3, and finalR = 0.028for 1010 reflections with I 
2.5
(I) and107 variables. Copper(I) arenethiolate 6 formsdark red crystals and isnonameric in the solid state as well as in solution. Crystals of{[Cu(S-1-C10H6NMe2-8)]9}2{C6H6}10.5(6), C279H279Cu18N18S18, are triclinic, spacegroup P
, with a = 16.081(2) Å,b = 26.650(4) Å, c = 32.747(6) Å,
=67.320(13)
, 
= 76.180(12), 
= 81.226(12),V = 12545(4) Å3, Z = 2, andfinal R = 0.118 for 28749 reflectionsand 1501 variables. Reaction of nonameric 6 with(3,3-dimethylbutynyl)copper results in the formation ofthe2:1 mixed dimeric hexanuclear organo(arenethiolato)copperaggregate[Cu3(S-1-C10H6NMe2-8)2(C
CtBu)]2(9),C60H66Cu6N4S4,which has been isolated as an air-stable orange solid which isinsoluble in most common organicsolvents. Crystals of 9 are monoclinic, space groupP21/c, with a = 11.9839(5) Å,b = 12.9391(8) Å, c =18.9482(7) Å, = 108.326(3), V =2789.1(2) Å3, Z = 2, and finalR = 0.0314 for 5110 reflections with I2.5(I) and 358 variables. Reaction of6 with mesitylcopper,[Cu5(C6H2Me3-2,4,6)5],results in the formation ofthe 1:1 mixed organo(arenethiolato)copper aggregate[Cu2(S-1-C10H6NMe2-8)(C6H2Me3-2,4,6)]n(10), which is ayellowish-brown, slightly air-sensitive solid that is soluble in polarand aromatic hydrocarbons. The new mixedaggregates 9 and 10 are thermodynamically andkinetically very stable, and it is found that the overallstructureof mixed organo(arenethiolato)copper aggregates such as9 is insensitive to structural changes in thearenethiolateligand.
2.5(I) and107 variables. Copper(I) arenethiolate 6 formsdark red crystals and isnonameric in the solid state as well as in solution. Crystals of{[Cu(S-1-C10H6NMe2-8)]9}2{C6H6}10.5(6), C279H279Cu18N18S18, are triclinic, spacegroup P, with a = 16.081(2) Å,b = 26.650(4) Å, c = 32.747(6) Å, =67.320(13), = 76.180(12), = 81.226(12),V = 12545(4) Å3, Z = 2, andfinal R = 0.118 for 28749 reflectionsand 1501 variables. Reaction of nonameric 6 with(3,3-dimethylbutynyl)copper results in the formation ofthe2:1 mixed dimeric hexanuclear organo(arenethiolato)copperaggregate[Cu3(S-1-C10H6NMe2-8)2(CCtBu)]2(9),C60H66Cu6N4S4,which has been isolated as an air-stable orange solid which isinsoluble in most common organicsolvents. Crystals of 9 are monoclinic, space groupP21/c, with a = 11.9839(5) Å,b = 12.9391(8) Å, c =18.9482(7) Å, = 108.326(3), V =2789.1(2) Å3, Z = 2, and finalR = 0.0314 for 5110 reflections with I2.5(I) and 358 variables. Reaction of6 with mesitylcopper,[Cu5(C6H2Me3-2,4,6)5],results in the formation ofthe 1:1 mixed organo(arenethiolato)copper aggregate[Cu2(S-1-C10H6NMe2-8)(C6H2Me3-2,4,6)]n(10), which is ayellowish-brown, slightly air-sensitive solid that is soluble in polarand aromatic hydrocarbons. The new mixedaggregates 9 and 10 are thermodynamically andkinetically very stable, and it is found that the overallstructureof mixed organo(arenethiolato)copper aggregates such as9 is insensitive to structural changes in thearenethiolateligand.