Syntheses, 95Mo NMR Spectroscopy and Structures of Distorted Cubic Mo4(μ3-O)4(μ2-O2P(CH2C6H5)2)4O4 and the Open Mixed-Valent Cluster, Mo4(μ3-O)2 (μ2-O2P(CH2C6H5)2)6O6

被引：10
|
作者：
Maass, John S. [1 ]
Zeller, Matthias [2 ]
Holmes, Daniel [3 ]
Bayse, Craig A. [4 ]
Luck, Rudy L. [1 ]
机构：
[1] Michigan Technol Univ, Dept Chem, Houghton, MI 49931 USA
[2] Youngstown State Univ, Dept Chem, Youngstown, OH 44555 USA
[3] Michigan State Univ, Dept Chem, E Lansing, MI 48824 USA
[4] Old Dominion Univ, Dept Chem & Biochem, Norfolk, VA 23529 USA
来源：
JOURNAL OF CLUSTER SCIENCE | 2011年 / 22卷 / 02期
关键词：
Mo-95; NMR; Phosphinate ligands; Molybdenum clusters; Mixed-valent compound; Cubic arrangements; DFT calculations; GIAO-DFT; PHOSPHINE OXIDE LIGANDS; CRYSTAL-STRUCTURES; MOLECULAR CALCULATIONS; MOLYBDENUM PHOSPHATE; BASIS-SETS; COMPLEXES; TETRANUCLEAR; OCTAMOLYBDATE; EPOXIDATION; CHEMISTRY;
D O I：
10.1007/s10876-011-0373-7
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reaction of MoO2(acac)(2) and dibenzylphosphinic acid in ethanol leads to a red distorted cubic tetrameric cluster, Mo-4(mu(3)-O)(4)(mu(2)-O2P(CH2C6H5)(2))(4)O-4, and a pink open mixed-valent cluster, Mo-4(mu(3)-O)(2)(mu(2)-O2P(CH2C6H5)(2))(6)O-6, when the reduction is carried out at 120 and 75 degrees C, respectively. Mo-95 NMR spectroscopy revealed a singlet for Mo-4(mu(3)-O)(4)(mu(2)-O2P(CH2C6H5)(2))(4)O-4 (1) at 584.9 ppm (Delta(v1/2) = 4500 Hz) and two resonances for Mo-4(mu(3)-O)(2)(mu(2)-O2P(CH2C6H5)(2))(6)O-6 (2) at 238.8 ppm (Delta(v1/2) = 1250 Hz) and 6.4 ppm (Delta(v1/2) = 5999 Hz), which were assigned to the Mo(V) and Mo(VI) sites, respectively. DFT geometries and Mo-95 DFT-GIAO chemical shifts for Mo-4(mu(3)-O)(4)(mu(2)-O2P(CH3)(2))(4)O-4 (3) and Mo-4(mu(3)-O)(2)(mu 2-O2P(CH3)(2))(6)O-6 (4) are consistent with X-ray crystallography and Mo-95 NMR of 1 and 2. The open complex, Mo-4(mu(3)-O)(2)(mu(2)-O2P(CH2C6H5)(2))(6)O-6 center dot 2(CH2Cl2), exhibits a central Mo(V)-Mo(V) single bond at 2.6217(5) angstrom with each Mo(V) atom bonded to one oxo (trans-disposed) terminal ligand.
引用
收藏
页码：193 / 210
页数：18
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