Preparation of [Mo2(O2CCH3)4] and [CrMo(O2CCH3)4] from MII derivatives (M = Cr, Mo)

doi:10.1016/S0277-5387(00)86902-8

Polyhedron

Volume 9, Issue 9, 1990, Pages 1237-1239

https://doi.org/10.1016/S0277-5387(00)86902-8 Get rights and content

Abstract

The compounds [Mo₂(O₂CCH₃)₄] and [CrMo(O₂CCH₃)₄] are conveniently prepared in 40–50% yields from acetic acid/acetic anhydride solutions and respectively, [Mo₂Br₄(CO)₈] or a mixture of [Mo₂Br₄(CO)₈] and CrCI₂. An improvement in the preparation of [Mo₂(O₂CCH₃)₄] from Mo(CO)₆ and acetic acid is also described.

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Cited by (7)

Theoretical study on the diradical characters and third-order nonlinear optical properties of transition-metal heterodinuclear systems
2013, Chemical Physics Letters
Citation Excerpt :
Although complexes involving the Cr(II)−Mo(II) system exist [38–40], those involving Cr(II)−Mn(III) as well as the corresponding homodinuclear system, Mn(III)−Mn(III), have not yet been synthesized. By contrast, complexes involving the Tc(III)−Tc(III) system have been prepared [41–43], which gave us the impetus to examine the Cr(II)−Tc(III) model system. It is predicted that Cr(II)−Tc(III) is less asymmetric than Cr(II)−Mn(III) because the dz2 orbital energy of Tc(III) (−1.5698 a.u.) is higher than that of Mn(III) (−1.9473 a.u.) and the charge transfer amount from Cr(II) to Tc(III) in Cr(II)−Tc(III) (at R = 2.2 Å) goes down to 0.1460e. So, the asymmetricity of Cr(II)−Tc(III) lies between those of Cr(II)–Mo(II) and Cr(II)–Mn(III).
We investigate the correlation between the diradical characters and the second hyperpolarizabilities (γ) of several transition-metal heterodinuclear systems using the spin-unrestricted coupled-cluster method. Due to asymmetry, the longitudinal γ values are enhanced by the primary contribution of the dσ electrons with intermediate diradical character. In particular, large enhancements of γ amplitudes and/or change of signs are found for the systems composed of different group metal atoms due to the large asymmetric charge distribution originating from the difference in their ionization potentials. This result indicates a possibility of a novel class of efficient nonlinear optical materials based on transition-metal heterodinuclear complexes.
Dinuclear Metal-Metal Bonded Systems
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Formation of isopolyoxometallate(VI) anions in the reaction between M(CO)<inf>6</inf> (M = W, Mo) and acetic acid: x-ray crystal structure of [W<inf>3</inf>(μ<inf>3</inf>-O)<inf>2</inf>(μ<inf>2</inf>η<sup>2</sup>-O<inf>2</inf>CCH<inf>3</inf>)<inf>6</inf>(H<inf>2</inf>O)<inf>3</inf>]<inf>2</inf>[W<inf>10</inf>O<inf>32</inf>·solvent
1993, Polyhedron
W(CO)₆ reacts with a mixture of acetic acid/acetic anhydride to give [W₃ (μ₃-O)₂(μ₂η²-O₂CCH₃)₆(H₂O)₃](CH₃CO₂)₂ (1), which was converted by HClO₄ to [W₃ (μ₃-O)₂(μ₂η²-O₂CCH₃)₆(H₂O)₃](ClO₄)₂ (2). Addition of CH₃CO₂Na to the above reaction mixture, and prolonged exposure of the solution to air, results in the formation of the W^IV/W^VI complex salt [W₃(μ₃-O)₂(μ₂η²-O₂CCH₃)₆(H₂O)₃]₂[W₁₀O₃₂]·solvent (3). Complex 3 was also prepared by reacting 1 with Na₂WO₄·2H₂O in acetic acid, and it has been characterized by X-ray crystallography. Addition of [CH₃(CH₂)₃]₄N(ClO₄) to the reaction filtrate remaining after the preparation of [Mo₂(μ-O₂CCH₃)₄][from Mo(CO)₆, CH₃CO₂H and (CH₃CO)₂O], followed by exposure to air, gives ([CH₃(CH₂)₃]₄N)₂[Mo₆O₁₉] (4).
Olefins by transition metal catalyzed elimination reactions from tertiary alcohols and acetates
1991, Tetrahedron
Heterodinuclear transition-metal complexes with multiple metal-metal bonds
2002, Angewandte Chemie - International Edition
Solvent stabilized transition metal cations as initiators for cyclopentadiene polymerization
1999, Macromolecular Rapid Communications

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CommunicationPreparation of [Mo2(O2CCH3)4] and [CrMo(O2CCH3)4] from MII derivatives (M = Cr, Mo)

Abstract

Z. Anorg. Allg. Chem.

J. Am. Chem. Soc.

Polyhedron

Inorg. Synth.

Communication
Preparation of [Mo₂(O₂CCH₃)₄] and [CrMo(O₂CCH₃)₄] from M^II derivatives (M = Cr, Mo)