Mo(4)(η(3)-烯丙基)(4)Cl(2)(OH)(2)(CO)(8)：首个具有μ(3)-OH和μ(3)-Cl桥的立方烷型二价钼有机金属配合物。

Mo(4)(eta(3)-allyl)(4)Cl(2)(OH)(2)(CO)(8): the first cubane-type Mo(2+) organometallic complex with mu(3)-OH and mu(3)-Cl bridges.

作者信息

Amarante Tatiana R, Gonçalves Isabel S, Almeida Paz Filipe A

机构信息

Department of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal.

出版信息

Acta Crystallogr C. 2009 Apr;65(Pt 4):m168-70. doi: 10.1107/S0108270109009512. Epub 2009 Mar 28.

DOI:10.1107/S0108270109009512

PMID:19346604

Abstract

The reaction between fluorenyllithium and Mo(eta(3)-C(3)H(5))Cl(NCMe)(2)(CO)(2) led to the isolation of di-mu(3)-chlorido-di-mu(3)-hydroxido-tetrakis[(eta(3)-allyl)dicarbonylmolybdenum(II)]-9-fluorenone-tetrahydrofuran (1/1/1), [Mo(4)(C(3)H(5))(4)Cl(2)(OH)(2)(CO)(8)].C(4)H(8)O.C(13)H(8)O. The tetrametallic Mo(4) unit constitutes the first example of a complex containing simultaneously two mu(3)-OH groups and two mu(3)-Cl anions capping the metallic trigonal prism. The four crystallographically independent Mo(2+) centres exhibit distorted octahedral geometry with the eta(3)-allyl groups being trans-coordinated to a mu(3)-OH group and the carbonyl groups occupying the equatorial plane. Space-filling tetrahydrofuran and 9-fluorenone molecules are engaged in strong O-H...O hydrogen-bonding interactions with Mo(4)(eta(3)-allyl)(4)Cl(2)(OH)(2)(CO)(8) complexes.

摘要

芴基锂与Mo(η³-C₃H₅)Cl(NCMe)₂(CO)₂反应，得到了二-μ₃-氯代-二-μ₃-羟基-四[(η³-烯丙基)二羰基钼(II)]-9-芴酮-四氢呋喃(1/1/1)，即[Mo₄(C₃H₅)₄Cl₂(OH)₂(CO)₈]·C₄H₈O·C₁₃H₈O。四核钼单元Mo₄是首例同时含有两个μ₃-OH基团和两个μ₃-Cl阴离子封端金属三角棱柱的配合物。四个晶体学独立的Mo²⁺中心呈现出畸变的八面体几何构型，其中η³-烯丙基与一个μ₃-OH基团反式配位，羰基占据赤道平面。空间填充的四氢呋喃和9-芴酮分子与Mo₄(η³-烯丙基)₄Cl₂(OH)₂(CO)₈配合物存在强烈的O-H...O氢键相互作用。