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Synthesis and Structure of the Tetrameric [Cp*V(μ‐F) 2 ] 4 (Cp* = C 5 Me 5 ); Preparation of the Imido Molybdenum Fluoride [(2,6‐ i ‐Pr 2 C 6 H 3 N) 2 MoF 2 ] · THF and the Structural Investigation of [(2,6‐ i ‐Pr 2 C 6 H 3 N) 6 Mo 4 (μ 3 ‐F) 2 Me 2 (μ‐O) 4 ]
Author(s) -
Hao Haijun,
Roesky Herbert W.,
Cui Chunming,
Schmidt HansGeorg,
Noltemeyer Mathias,
Yu Peihua,
Bai Guangcai
Publication year - 2000
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(200002)626:2<368::aid-zaac368>3.0.co;2-r
Subject(s) - crystallography , octahedron , chemistry , crystal structure , molybdenum , trigonal bipyramidal molecular geometry , bond length , bipyramid , atom (system on chip) , oxygen atom , stereochemistry , molecule , inorganic chemistry , organic chemistry , computer science , embedded system
Treating [Cp*V(μ‐Cl) 2 ] 3 (Cp* = C 5 Me 5 ) and [(2,6‐ i ‐Pr 2 C 6 H 3 N) 2 MoMe 2 ], respectively, with Me 3 SnF afforded the title compounds [Cp*V(μ‐F) 2 ] 4 ( 1 ) and [(2,6‐ i ‐Pr 2 C 6 H 3 N) 2 MoF 2 ] · THF ( 2 ). 1 has a tetrameric structure, in which four V atoms can be regarded as being arranged at the vertices of a distorted tetrahedron, with four long edges bridged by one F atom and each of the other two short edges bridged by two F atoms with a mean V–F bond length of 2.00 Å. A hydrolyzed product of 2 , [(2,6‐ i ‐Pr 2 C 6 H 3 N) 6 Mo 4 (μ 3 ‐F) 2 Me 2 (μ‐O) 4 ] ( 3 ) was characterized by elemental analyses and X‐ray single crystal study. The X‐ray diffraction analysis reveals that 3 has a unique tetranuclear structure, containing two five and two six coordinated Mo atoms connecting each other by four μ‐O and two μ 3 ‐F atoms. The geometries around the two Mo atoms can be described having distorted trigonal bipyramidal and distorted octahedral coordination spheres, respectively. The Mo–(μ‐O) bond lengths are 1.813 Å (average) for five coordinated Mo atoms and 2.030 Å (average) for those of six coordinated, respectively, indicating an additional π bonding between five coordinated Mo atoms and the μ‐O atoms. The Mo–(μ 3 ‐F) distances range from 2.291 to 2.352 Å.