Mixed-ligand compounds incorporating quadruply bonded dimolybdenum(II) core: Syntheses, structures and reactivity studies

作者：Majumdar Moumita; Rahaman S M Wahidur; Sinha Arup; Bera Jitendra K^*

来源：Inorganica Chimica Acta, 2010, 363(12): 3078-3087.

DOI：10.1016/j.ica.2010.03.044

• Naphthyridine
• Metal-metal bond
• Molybdenum
• Mixed-ligand compound
• Metal-oxo compound

Reaction of cis-[Mo(2)(OAc)(2)(CH(3)CN)(6)][BF(4)](2) with NP-Et, Me (2-ethyl-3-methyl-1,8-naphthyridine) in acetonitrile provides trans-[Mo(2)(NP-Et, Me)(2)(OAc)(2)(CH(3)CN)][BF(4)](2) (1). Partial protonation of 1 by HBF(4)center dot Et(2)O in acetonitrile leads to trans-[Mo(2)(NP-Et, Me)(2)(OAc)(CH(3)CN)(3)][BF(4)](3) (2). In both compounds, NP-R ligands are arranged in a head-to-head (HH) fashion leaving one of the axial sites vacant. Substitution of acetonitriles by NP-Me (3-methyl-1,8-naphthyridine) in trans-[Mo(2)(NP-tz)(2)(OAc)(CH(3)CN)(2)][BF(4)](3) provides trans-[Mo2(NP-tz) 2(OAc)(NP-Me)][BF4] 3 (3) with retention of configuration. Fully solvated dimolybdenum( II) compound reacts with NP-NH(2) to provide [Mo(2)(NP-NH(2))(2)(NP-NH)(CH(3)CN)(2)][BF(4)](3) (4) in which the NP-NH(2) ligands are trans and arranged in a HH fashion. The deprotonated ligand (NP-NH ) binds the dimetal unit utilizing naphthyridine nitrogen and amido nitrogen. Treatment of [Mo(2)(NP-tz) (2)(CH(3)CN)(4)][CF(3)SO(3)](4) with bpym (2,2'-bipyrimidine) followed by crystallization in air provided an oxo complex [Mo(2)(NP-tz)(2)(mu(2)-O)(2)(bpym)(2)][CF(3)SO(3)](4) (5). Compounds 1-5 have been characterized by a variety of spectroscopic techniques and by X-ray crystallography. The reactivity pattern is rationalized based on ligand labilities and thermodynamic stabilities.

• 出版日期2010-10-15