新型铁和钌二炔基配合物的制备、结构及一些反应

Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium.

作者信息

Bruce Michael I, Ellis Benjamin G, Gaudio Maryka, Lapinte Claude, Melino Giovanni, Paul Frédéric, Skelton Brian W, Smith Mark E, Toupet Loic, White Allan H

机构信息

Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005.

出版信息

Dalton Trans. 2004 May 21(10):1601-9. doi: 10.1039/b316297b. Epub 2004 Apr 19.

DOI:10.1039/b316297b

PMID:15252610

Abstract

Reactions between HC triple bond CC triple bond CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C triple bond CC triple bond CSiMe3)(L2)Cp'[Cp'= Cp, L = CO (1), PPh3 (2); Cp' = Cp*, L2= dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(C triple bond CC triple bond CH)(L2)Cp'[Cp'= Cp, L = PPh3 (5); Cp'= Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3)2 to give Ru(C triple bond CC triple bond CAu(PR3)](L2)Cp'[Cp' = Cp, L = PPh3, R = Ph (7); Cp' = Cp*, L2= dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped [Cp(Ph3P)2Ru]C triple bond CC triple bond C[Ru(dppe)Cp*] (10) was obtained from Ru(C triple bond CC triple bond CH)(dppe)Cp* and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of and are reported, with a comparative determination of the structure of Fe(C triple bond CC triple bond CSiMe3)(dppe)Cp* (4), and those of a fifth polymorph of [Ru(PPh3)2Cp]2(mu-C triple bond CC triple bond C) (12), and [Ru(dppe)Cp]2(mu-C triple bond CC triple bond C) (13).

摘要

HC≡CC≡CSiMe₃与几种卤化钌前驱体之间的反应得到了配合物Ru(C≡CC≡CSiMe₃)(L₂)Cp'[Cp' = Cp，L = CO (1)，PPh₃ (2)；Cp' = Cp*，L₂ = dppe (3)]。2和3的原硅基脱除反应得到了未取代的丁-1,3-二炔-1-基配合物Ru(C≡CC≡CH)(L₂)Cp'[Cp' = Cp，L = PPh₃ (5)；Cp' = Cp*，L₂ = dppe (6)]。在KN(SiMe₃)₂存在下，5或6中的H被Au(PR₃)基团取代，反应得到Ru(C≡CC≡CAu(PR₃)](L₂)Cp'[Cp' = Cp，L = PPh₃，R = Ph (7)；Cp' = Cp*，L₂ = dppe，R = Ph (8)，tol (9)]。不对称端基封端的[Cp(Ph₃P)₂Ru]C≡CC≡C[Ru(dppe)Cp*] (10)由Ru(C≡CC≡CH)(dppe)Cp和RuCl(PPh₃)₂Cp制得。报道了相关配合物的单晶X射线结构测定结果，并对Fe(C≡CC≡CSiMe₃)(dppe)Cp (4)、[Ru(PPh₃)₂Cp]₂(μ-C≡CC≡C) (1第十二种多晶型物以及[Ru(dppe)Cp]₂(μ-C≡CC≡C) (13)的结构进行了对比测定。