RING-METHYL ACTIVATION IN PENTAMETHYLCYCLOPENTADIENYL COMPLEXES .4. SYNTHESES, STRUCTURES, AND REACTIONS OF [(C(5)ME(4)CH(2)CL)RUCL(CO)(2)] AND RELATED-COMPOUNDS - X-RAY STRUCTURES OF [(C(5)ME(4)CH(2)CL)RUCL(CO)(2)] AND[(C(5)ME(4)CH(2)OET)RU(PPH(3))(CO)(2)](OTF)

被引：36

作者：

FAN, L ^{[1
]}

TURNER, ML ^{[1
]}

ADAMS, H ^{[1
]}

BAILEY, NA ^{[1
]}

MAITLIS, PM ^{[1
]}

机构：

[1] UNIV SHEFFIELD,DEPT CHEM,SHEFFIELD S3 7HF,S YORKSHIRE,ENGLAND

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 02期

关键词：

D O I：

10.1021/om00002a015

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The dicarbonyl chloro complex [(C(5)Me(4)CH(2)Cl)RuCl(CO)(2)] (4) is formed by carbonylation (1 atm, 20 degrees C, 5 min) of the dimeric tetramethylfulvene complex [{(C(5)Me(4)CH(2))RUCl(2)}(2)] (3), which is in turn made by oxygenation (1 atm, 20 degrees C, 30 min) of [{(C(5)Me(5))RUCl(2)}(2)] (1); since both reactions proceed in high yield, 4 is a readily accessible starting material for a range of Cp*-substituted ruthenium complexes. The C-Cl in 4 is readily substituted by nucleophiles to give [(C(5)Me(4)CH(2)X)Ru(CO)(2)Cl] (X = OH, OMe, OEt, O-i-Pr, OPh, OCH(2)Ph, NEt(2), H), and by PPh(3) (in the presence of NH4PF6) to give [(C(5)Me(4)CH(2)PPh(3))Ru(CO)(2)Cl]PF6. The Ru-Cl in the alkoxy complexes [(C(5)Me(4)CH(2)OR)Ru(CO)(2)Cl] is replaced by reaction with KX to give [(C(5)Me(4)CH(2)OR)Ru(CO)(2)X] (R = Me, X = Br, I, CN, SCN; R = Et, X = Br, I) and by PPh(3) in the presence of Ag+ to give [(C(5)Me(4)CH(2)OEt)Ru(CO)(2)(PPh(3))](+). Reaction of 4 with KCN or KSCN in MeOH gave a mixture of [(C(5)Me(4)CH(2)OMe)Ru(CO)(2)X], [(C(5)Me(5))Ru(CO)(2)X], and [(C(5)Me(4)CH(2)X)Ru(CO)(2)X] (X = CN, SCN). The amines are quaternized; e.g., [(C(5)Me(4)CH(2)NEt(2))Ru(CO)(2)Cl] reacted with MeI to give [(C(5)Me(4)CH(2)NEt(2)Me)Ru(CO)(2)I]I. X-ray crystal structure determinations were carried out for [(C(5)Me(4)CH(2)Cl)Ru(CO)(2)Cl] (orthorhombic, a = 18.291(3) Angstrom, b = 11.087(17) Angstrom, c = 6.877(12) Angstrom, V = 1394.6(4) Angstrom(3), Z = 4, D-c = 1.725 g cm(-3), space group Pnma (D-2h(16), NO. 62)) and [(C(5)Me(4)CH(2)OEt)Ru(CO)(2)(PPh(3))](+)(OTf)(-) (triclinic, a = 10.496(12) Angstrom, b = 12.509(9) Angstrom, c 12.738(7) Angstrom, alpha = 90.25(5)degrees, beta = 93.56(7)degrees, gamma = 93.85(7)degrees, V = 1666(2) Angstrom(3), Z = 2, D-c = 1.491 g cm(-3), space group P ($) over bar 1 (C-i(1) No. 2)).

引用

页码：676 / 684

页数：9

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