Monomeric Alkyne-Stabilized Complexes of Organo-Copper(I) and -Silver(I)
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- 作者：Heinrich Lang ; Katrin Kö ; hler ; Gerd Rheinwald ; Laszlo Zsolnai ; Michael Bü ; chner ; Alexander Driess ; Gottfried Huttner ; and Joachim Strä ; hle
- 刊名：Organometallics
- 出版年：1999
- 出版时间：February 15, 1999
- 年：1999
- 卷：18
- 期：4
- 页码：598 - 605
- 全文大小：164K
- 年卷期：v.18,no.4(February 15, 1999)
- ISSN：1520-6041
文摘
The synthesis of heterobimetallic {[Ti](C
CR1)2}MX {[Ti] = (
5-C5H4SiMe3)2Ti; M = Cu,R1 = SiMe3: 4a, X = SCF3; 4b, X = SEt; M = Ag, R1 = tBu: 5a, X = OC(O)Me; 5e, X = NO3;M = Ag, R1 = SiMe3: 5b, X = OC(O)Me; 5c, X = OC(O)Ph; 5d, X = NO3} is described.These compounds together with {[Ti](CCR1)2}CuX (4c, R1 = SiMe3, X = SC6H4CH2NMe2-2; 4d, R1 = tBu, X = SC6H4CH2NMe2-2) can be used for the preparation of a large variety ofdifferent organo-copper(I) and -silver(I) species. The titanium-copper complexes {[Ti](CCR1)2}CuR2 [R1 = SiMe3: 6a, R2 = C6F5; 6b, R2 = C6H2(CF3)3-2,4,6; 6c, R2 = C6H2Ph3-2,4,6;R1 = tBu: 6d, R2 = C6H2Ph3-2,4,6; 7, R2 = Me] are accessible by the reaction of 4c or 4dwith suitable organic nucleophiles. Monomeric organo-silver(I) compounds can be preparedby using different starting materials: While the silver(I) aryls {[Ti](CCSiMe3)2}AgR2 [8a,R2 = C6H2(CF3)3-2,4,6; 8b, R2 = C6H2Ph3-2,4,6] are only available by the reaction of 5b withLiC6H2(CF3)3-2,4,6 or BrMgC6H2Ph3-2,4,6, the silver(I) methyl species {[Ti](CCR1)2}AgMe(9a, R1 = SiMe3; 9b, R1 = tBu) can be synthesized by using 5a, 5b, 5d, or 5e as startingmaterials. While compounds 6-8 are stable under the reaction conditions applied, 9a alreadystarts to decompose at low temperature: The heterobimetallic titanium-silver acetylide{[Ti](CCSiMe3)(CCAg)}2 (10) is formed by nucleophilic substitution of one of the alkynylMe3Si groups, whereby SiMe4 is eliminated. Moreover, compounds 6-9 react with Br2 toproduce R2-Br along with {[Ti](CCR1)2}MBr (M = Cu; 11a, R1 = tBu; 11b, R1 = SiMe3; M= Ag, 11c, R1 = SiMe3), which yield with equimolar amounts of LiR2 or BrMgR2 the startingmaterials 6-9 back.The solid-state structures of 4a, 5c, 6c, and 8b are reported. Allcomplexes contain a monomeric (2-alkyne)2M(1-X) (4, 5) or (2-alkyne)2M(1-R2) (6-9) entityin which the group 11 metal atom M is trigonally coordinated by the two alkynyl ligandsCCR1 and the 1-bonded groups X or R2, respectively.
CR1)2}MX {[Ti] = (5-C5H4SiMe3)2Ti; M = Cu,R1 = SiMe3: 4a, X = SCF3; 4b, X = SEt; M = Ag, R1 = tBu: 5a, X = OC(O)Me; 5e, X = NO3;M = Ag, R1 = SiMe3: 5b, X = OC(O)Me; 5c, X = OC(O)Ph; 5d, X = NO3} is described.These compounds together with {[Ti](CCR1)2}CuX (4c, R1 = SiMe3, X = SC6H4CH2NMe2-2; 4d, R1 = tBu, X = SC6H4CH2NMe2-2) can be used for the preparation of a large variety ofdifferent organo-copper(I) and -silver(I) species. The titanium-copper complexes {[Ti](CCR1)2}CuR2 [R1 = SiMe3: 6a, R2 = C6F5; 6b, R2 = C6H2(CF3)3-2,4,6; 6c, R2 = C6H2Ph3-2,4,6;R1 = tBu: 6d, R2 = C6H2Ph3-2,4,6; 7, R2 = Me] are accessible by the reaction of 4c or 4dwith suitable organic nucleophiles. Monomeric organo-silver(I) compounds can be preparedby using different starting materials: While the silver(I) aryls {[Ti](CCSiMe3)2}AgR2 [8a,R2 = C6H2(CF3)3-2,4,6; 8b, R2 = C6H2Ph3-2,4,6] are only available by the reaction of 5b withLiC6H2(CF3)3-2,4,6 or BrMgC6H2Ph3-2,4,6, the silver(I) methyl species {[Ti](CCR1)2}AgMe(9a, R1 = SiMe3; 9b, R1 = tBu) can be synthesized by using 5a, 5b, 5d, or 5e as startingmaterials. While compounds 6-8 are stable under the reaction conditions applied, 9a alreadystarts to decompose at low temperature: The heterobimetallic titanium-silver acetylide{[Ti](CCSiMe3)(CCAg)}2 (10) is formed by nucleophilic substitution of one of the alkynylMe3Si groups, whereby SiMe4 is eliminated. Moreover, compounds 6-9 react with Br2 toproduce R2-Br along with {[Ti](CCR1)2}MBr (M = Cu; 11a, R1 = tBu; 11b, R1 = SiMe3; M= Ag, 11c, R1 = SiMe3), which yield with equimolar amounts of LiR2 or BrMgR2 the startingmaterials 6-9 back.The solid-state structures of 4a, 5c, 6c, and 8b are reported. Allcomplexes contain a monomeric (2-alkyne)2M(1-X) (4, 5) or (2-alkyne)2M(1-R2) (6-9) entityin which the group 11 metal atom M is trigonally coordinated by the two alkynyl ligandsCCR1 and the 1-bonded groups X or R2, respectively.