Imido-supported borohydrides of titanium, vanadium and molybdenum

Andrey Y. Khalimon; Erik Peterson; Christian Lorber; Lyudmila G. Kuzmina; Judith A.K. Howard; Art Van Der Est; Georgii I. Nikonov

doi:10.1002/ejic.201201351

Imido-supported borohydrides of titanium, vanadium and molybdenum

Andrey Y. Khalimon, Erik Peterson, Christian Lorber, Lyudmila G. Kuzmina, Judith A.K. Howard, Art Van Der Est, Georgii I. Nikonov

Department of Chemistry

Research output: Contribution to journal › Article

6 Citations (Scopus)

Abstract

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 d_xy orbital of Ti. In contrast, the d_xy 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.

Original language	English
Pages (from-to)	2205-2211
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	12
DOIs	https://doi.org/10.1002/ejic.201201351
Publication status	Published - Apr 1 2013

Keywords

Borohydrides
Imides
Molybdenum
Titanium
Vanadium

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.201201351

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Khalimon, A. Y., Peterson, E., Lorber, C., Kuzmina, L. G., Howard, J. A. K., Van Der Est, A., & Nikonov, G. I. (2013). Imido-supported borohydrides of titanium, vanadium and molybdenum. European Journal of Inorganic Chemistry, (12), 2205-2211. https://doi.org/10.1002/ejic.201201351

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title = "Imido-supported borohydrides of titanium, vanadium and molybdenum",

abstract = "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.",

keywords = "Borohydrides, Imides, Molybdenum, Titanium, Vanadium",

author = "Khalimon, {Andrey Y.} and Erik Peterson and Christian Lorber and Kuzmina, {Lyudmila G.} and Howard, {Judith A.K.} and {Van Der Est}, Art and Nikonov, {Georgii I.}",

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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.

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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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