炔基金属配合物中 C[三重键]C 到 CO 的转化：碳链被三钴簇封端的氧化。

Conversion of C[triple bond]C to CO in alkynyl-metal complexes: oxidation of carbon chains capped by carbon-tricobalt clusters.

机构信息

School of Chemistry & Physics, University of Adelaide, Adelaide, South Australia5005.

出版信息

Dalton Trans. 2010 Oct 7;39(37):8801-11. doi: 10.1039/c002997c. Epub 2010 Aug 12.

PMID:20714481

Abstract

Treatment of Co(3)(mu(3)-CC[triple bond]CR)(mu-dppm)(CO)(7) with O(2) (air) in the presence of [FcH]PF(6) afforded Co(3){mu(3)-CC(O)R}(mu-dppm)(CO)(7) by the formal conversion -C[triple bond]C- + O-O --> >C-O + C[triple bond]O. In this way, complexes with R = Ph, Fc, and W(CO)(3)Cp, bis-clusters {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[triple bond]C(O)(C[triple bond]C)C[triple bond]]}, {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[triple bond]C(O)(C[triple bond]C)(x)C(O)C[triple bond, length as m-dash]]} (x = 1, 2), and {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[triple bond]CC(O)C[triple bond, length as m-dash]CC(6)H(4)C[triple bond]CC(O)C[triple bond]]}, and heterometallic bis-clusters {Co(3)(mu-dppm)(CO)(7)}{mu(3):mu(3)-[[triple bond]CC(O)C[triple bond]CC[triple bond]]}{M(3)(mu-H)(3)(CO)(9)} (M = Ru, Os) have been prepared. Single-crystal XRD structure determinations of several products are reported together with that of precursor {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[triple bond]C(C[triple bond]C)(2)C(6)H(4)(C[triple bond]C)(2)C[triple bond]]}.

摘要

用 O(2)（空气）处理 Co(3)(mu(3)-CC[三重键]CR)(mu-dppm)(CO)(7)，在 [FcH]PF(6)的存在下，通过 -C[三重键]C- + O-O 的正式转化得到 Co(3){mu(3)-CC(O)R}(mu-dppm)(CO)(7)，生成 >C-O + C[三重键]O。通过这种方式，得到了 R = Ph、Fc 和 W(CO)(3)Cp 的配合物，双簇 {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[三重键]C(O)(C[三重键]C)C[三重键]]}，{Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[三重键]C(O)(C[三重键]C)(x)C(O)C[三重键]]}（x = 1，2），和 {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[三重键]CC(O)C[三重键, length as m-dash]CC(6)H(4)C[三重键]CC(O)C[三重键]]}，以及杂金属双簇 {Co(3)(mu-dppm)(CO)(7)}{mu(3):mu(3)-[[三重键]CC(O)C[三重键]CC[三重键]]}{M(3)(mu-H)(3)(CO)(9)}（M = Ru，Os）。报道了几种产物的单晶 XRD 结构测定结果，并报道了前体 {Co(3)(mu-dppm)(CO)(7)}(2){mu(3):mu(3)-[[三重键]C(C[三重键]C)(2)C(6)H(4)(C[三重键]C)(2)C[三重键]]}的结构。