NOVEL REACTIVITIES OF TERMINAL DIACETYLIDES ON THE THIOLATE-BRIDGED DIRUTHENIUM CENTER - THEIR CHEMICAL-TRANSFORMATIONS INTO DIRUTHENACYCLOPENTADIENOINDANE STRUCTURE AND 1,4-DISUBSTITUTED 1,3-DIYNES

被引：57

作者：

MATSUZAKA, H ^{[1
]}

HIRAYAMA, Y ^{[1
]}

NISHIO, M ^{[1
]}

MIZOBE, Y ^{[1
]}

HIDAI, M ^{[1
]}

机构：

[1] UNIV TOKYO,DEPT SYNTHET CHEM,TOKYO 113,JAPAN

来源：

ORGANOMETALLICS | 1993年 / 12卷 / 01期

关键词：

D O I：

10.1021/om00025a012

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Paramagnetic complex Cp*Ru(mu2-SPri)3RuCp* (1) (Cp* = eta5-C5Me5) reacts with terminal alkynes at room temperature to give the diamagnetic dinuclear terminal diacetylide complexes Cp*Ru(C=CR)(mu2-SPri)2Ru(C=CR)Cp* (2) (2a, R = Tol; 2b, R = Ph; 2c, R - CH(CH2)3CH2). Similar treatment of 1 with HC=CBut affords the dinuclear monoacetylide complex Cp*Ru-(C=CBut)mu2-SPri)2Ru(SPri)Cp* (3), which further reacts with terminal alkynes at 90-degrees-C to form the (mixed) diacetylide complexes Cp*Ru(C=CBut)(mu2-SPri)2Ru(C=CR)Cp* (4a, R = Tol; 4b, R = Ph; 4c, R = C=CH(CH2)3CH2; 2d; R = But). Complexes 2a and 2b readily react with HBF4 to give the diruthenacyclopentadienoindans complexes 5a and 5b in excellent yield, respectively, which have been formed by the coupling of two terminal acetylide ligands on the thiolate-bridged diruthenium center accompanied by aromatic C-H bond activation. Quantitative [GRAPHICS] deprotonation reactions of 5a and 5b smoothly proceed to give the diruthenacyclopentenoindene complexes 6a and 6b, respectively. Complexes 6a and 6b can be readily protonated with HBF4 to reproduce 5a and Sb. The mechanisms is proposed for these transformations. On the other hand, reactions of complexes 2a and 2b with 12 yield 1,4-disubstituted 1,3-butadiynes RC=CC=CR (9a, R - Tol; 9b, R = Ph) and Cp*Ru(I)(mu2-SPri)2Ru(I)Cp* (10). Complexes 2a, 5a, and 6a have been crystallographically characterized: 2a, P2,/n (monoclinic), a - 19.484 (7) angstrom, b - 19.291 (13) angstrom, c = 10.953 (4) angstrom, beta = 91.35 (3)-degrees, Z - 4, R - 0.099, R, = 0.11; 5a; P2(1)2(1)2(1) (orthorhombic), a = 16.391 (9) angstrom, b = 19.476 (7) angstrom, c - 13.055 (5) A, Z = 4, R - 0.078, R(w) = 0.092; 6a; P2,/n (monoclinic), a = 10.754 (2) angstrom, b = 19.536 (3) angstrom, c - 19.013 (5) angstrom, beta = 97.27 (2)-degrees, Z = 4, R = 0.047, R(w) = 0.034.

引用

页码：36 / 46

页数：11

共 96 条

[1] INTRAMOLECULAR NUCLEOPHILIC-ATTACK AT THE ALPHA-CARBON ATOM OF A MU-3-ALKYNYL LIGAND IN A TRIOSMIUM CLUSTER [J].