TY - JOUR
T1 - Imido-supported borohydrides of titanium, vanadium and molybdenum
AU - Khalimon, Andrey Y.
AU - Peterson, Erik
AU - Lorber, Christian
AU - Kuzmina, Lyudmila G.
AU - Howard, Judith A.K.
AU - Van Der Est, Art
AU - Nikonov, Georgii I.
PY - 2013/4/1
Y1 - 2013/4/1
N2 - New imido bis(borohydride) complexes [(RN=)M(PMe3) 2(η2-BH4)2] [R = Ar, M = Ti (3); R = Ar, M = V (5); R = Ar, M = Mo (6); R = Ar′, M = Mo (7); Ar = 2,6-iPr2C6H3, Ar′ = 2,6-Me 2C6H3] were prepared by the reaction of dichlorides [(RN=)MCl2(PMe3)n] (M = Ti, n = 2; M = V, n = 2, M = Mo, n = 3) with LiBH4 (2 equiv) in THF. Compounds 3, 5, 6 and 7 were studied by IR spectroscopy and X-ray diffraction, and an EPR spectroscopy study was performed for paramagnetic compound 5. In 3, the two borohydride units are orthogonal to each other as a result of the overlap of an antiphase combination of B-H orbitals with the empty dxy orbital of Ti. In contrast, the dxy orbital of the metal atom is singly occupied in 5 and fully occupied in 6 and 7, and both borohydride ligands are oriented in the same way, with the B(μ-H2)M moieties orthogonal to the P-M-P vector.
AB - New imido bis(borohydride) complexes [(RN=)M(PMe3) 2(η2-BH4)2] [R = Ar, M = Ti (3); R = Ar, M = V (5); R = Ar, M = Mo (6); R = Ar′, M = Mo (7); Ar = 2,6-iPr2C6H3, Ar′ = 2,6-Me 2C6H3] were prepared by the reaction of dichlorides [(RN=)MCl2(PMe3)n] (M = Ti, n = 2; M = V, n = 2, M = Mo, n = 3) with LiBH4 (2 equiv) in THF. Compounds 3, 5, 6 and 7 were studied by IR spectroscopy and X-ray diffraction, and an EPR spectroscopy study was performed for paramagnetic compound 5. In 3, the two borohydride units are orthogonal to each other as a result of the overlap of an antiphase combination of B-H orbitals with the empty dxy orbital of Ti. In contrast, the dxy orbital of the metal atom is singly occupied in 5 and fully occupied in 6 and 7, and both borohydride ligands are oriented in the same way, with the B(μ-H2)M moieties orthogonal to the P-M-P vector.
KW - Borohydrides
KW - Imides
KW - Molybdenum
KW - Titanium
KW - Vanadium
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U2 - 10.1002/ejic.201201351
DO - 10.1002/ejic.201201351
M3 - Article
AN - SCOPUS:84876248747
SP - 2205
EP - 2211
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 12
ER -