Clusters as ligands .6. Mixed-metal cluster carboxylates of titanium and zirconium derived from (eta(5)-C5H5)M'(CO)(2)Co-2(CO)(6)(mu(3)-CCOOH), M' = Mo, W

被引：21

作者：

Shimomura, H ^{[1
]}

Lei, XJ ^{[1
]}

Shang, MY ^{[1
]}

Fehlner, TP ^{[1
]}

机构：

[1] UNIV NOTRE DAME,DEPT CHEM & BIOCHEM,NOTRE DAME,IN 46556

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 24期

关键词：

D O I：

10.1021/om9708384

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The cluster acid CpM'(CO)(2)Co-2(CO)(6)(mu(3)-CCOOH) (M' = Mo, W; Cp = eta(5)-C5H5), 1, has been synthesized in good yield from the protected (CO)(9)Co-3(mu(3)-CC(O)OR) cluster by metal fragment exchange followed by acid hydrolysis, The protonolysis of group 4 M(IV)(OR)(4) (M = Zr, Ti) organic alkoxides with this new duster add leads to trimetal cluster M(IV) alkoxycarboxylates. The products, which were isolated in good yield as crystalline substances and characterized spectroscopically as well as crystallographically, are Zr-2(mu-OH)(2){mu-CpMo(CO)(2)-CO2(CO)(6)(mu(3)-CCO2)}(2){eta(2)-CpMo(CO)(2)Co-2(CO)(6)(mu(3)-CCO2)}(4), 2; Ti-4(eta(3)-O)(4)(OR)(2))(4){mu-CpM'(CO)(2)-Co-2(CO)(6)(mu(3)-CCO2)}(4), 3 (M' = Mo, R = CH(CH2)(3), 3a; M' = W, R = CH(CH2)(3), 3b; M' = Mo, R = C2H5, 3c; M' = W, R = C2H5, 3d). Direct comparison of this chemistry with that of [(CO)(9)Co-3(mu(3)-CCO2)](-), which is of similar size, shows the importance of the electronic properties of the cluster substituent in the metal coordination chemistry of the carboxylate functionality. The exclusive binding of the proximal isomer of the cluster ligand (ep ring adjacent to the capping carbon) relative to the more stable distal isomer (Cp ring positioned away from the capping carbon) provides definitive evidence for the existence of a cluster electronic effect in the coordination properties of the attached [-CO2](-) group. The significantly different chemistry of cluster vs organic ligands arises in part from this electronic effect.

引用

页码：5302 / 5311

页数：10

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