Dinuclear and heteropolynuclear complexes containing Mo24+ units

R. Clérac, F. A. Cotton, K. R. Dunbar, C. A. Murillo, X. Wang

Research output: Contribution to journalArticlepeer-review

36 Scopus citations

Abstract

The quadruply bonded compound Mo2(DpyF)4 (1), where DpyF- is the anion of N,N′-di(2-pyridyl)formamidine, has been prepared by ligand substitution reactions of Mo2(OOCCF3)4 and either the neutral ligand, HDpyF, at ambient temperature or its lithium salt, LiDpyF, under refluxing conditions. An X-ray structural analysis shows that 1 has a paddlewheel structure with a Mo4-Mo distance of 2.1108(6) Å. Reaction of 1 with CoCl2 in methanol produces the paramagnetic compound [Mo2Co(DpyF)4][CoCl4]·2MeOH (2). The Co(II) atom in the cation [Mo2Co(DpyF)4]2+ resides on a low-spin hexacoordinate environment (S = 1/2) with a Co···Mo separation of 2.979(6) Å, suggesting there is no direct bonding interaction between the Co and Mo atoms. The Mo-Mo distance of 2.1096(5) Å is similar to that in 1. Reaction of 1 and CuCl in methanol yields [Mo2Cu4(DpyF)4Cl2] [CuCl2]2· 2MeOH·Et2O (3). In the cation there are two copper atoms on each side of the Mo2 core. Each is coordinated to two pyridyl nitrogen atoms of the cis DpyF- ligands and loosely bridged to the other by a chloride ion. As a result, the Cu(I) atoms are not aligned with the Mo2 unit. The Cu to Mo separations are in the range 3.003(1)-3.015(1) Å, and the Mo-Mo distance of 2.127(1) Å is comparable to those in 1 and 2.

Original languageEnglish
Pages (from-to)420-426
Number of pages7
JournalInorganic Chemistry
Volume40
Issue number3
DOIs
StatePublished - Jan 29 2001
Externally publishedYes

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