SIGNIFICANCE OF CARBENOID CHARACTER DURING THE PROTONATION OF 4-MEMBERED AND 5-MEMBERED DIRUTHENACYCLES FORMED FROM THE REACTION OF RU-2(ME(2)PCH(2)PME(2))(2)(CO)(5) WITH DIMETHYL ACETYLENEDICARBOXYLATE

被引：10

作者：

JOHNSON, KA ^{[1
]}

VASHON, MD ^{[1
]}

MOASSER, B ^{[1
]}

WARMKA, BK ^{[1
]}

GLADFELTER, WL ^{[1
]}

机构：

[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 01期

关键词：

D O I：

10.1021/om00001a063

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Protonation of the diruthenacyclobutene Ru-2(dmpm)2(CO)(4)[mu-eta(1):eta(1)-C-2(CO(2)Me)(2)] (dmpm = bis(dimethylphosphino)methane) resulted in stereoselective formation of the chelated (Z)alkenyl complex {Ru-2(dmpm)(2)(CO)(4)[C-2(H)(CO(2)Me)(2)]}[BF4], as deternnined by single-crystal X-ray crystallography (P2(1)2(1)2 (No. 18) space group, a = 15.61(2) Angstrom, b = 22.67(2) Angstrom, c = 9.34(1) Angstrom, V = 3308(5) Angstrom(3), Z = 4). Protonation of the diruthenacyclopentenone Ru-2(dmpm)(2)(CO)(4) [mu-C(O)C-2(CO(2)Me)(2)] occurs reversibly at the carbonyl oxygen of the bridging group, giving the corresponding diruthenacyclopentenol. The X-ray crystal structure of the solvated molecule [P2(1) (No. 4) space group, a = 16.010(7) Angstrom, b = 11.833(6) Angstrom, c = 19.450(8) Angstrom, beta = 103.44(3)degrees, V = 3584(5) Angstrom(3), Z = 4) and its unusual blue color suggest a highly delocalized pi-system between the two metals. Reaction of the metal hydride [HRu2(dmpm)(2)-(CO)(5)][BF4] with dimethyl acetylenedicarboxylate (DMAD) results in formation of a new C-H bond and a sigma-bound (E)-alkenyl ligand. This same (E)-alkenyl product can also be formed by addition of CO to and alkene isomerization of the chelated (Z)-alkenyl complex{Ru-2(dmpm)(2)(CO)(4)[C-2(H)(CO(2)Me)(2)]}[BF4].

引用

页码：461 / 470

页数：10

共 27 条

[1] PHOTOCHEMISTRY AND ELECTRONIC-STRUCTURE OF BIS(DICARBONYL(ETA-5-CYCLOPENTADIENYL)RUTHENIUM) AND ITS IRON ANALOG [J].