Stable Tertiary Phosphine Adducts of Alane

Frederick R. Bennett; Fiona M. Elms; Michael G. Gardiner; George A. Koutsantonis; Colin L. Raston; Nicholas K. Roberts

doi:10.1021/om00040a013

Stable Tertiary Phosphine Adducts of Alane

Frederick R. Bennett, Fiona M. Elms, Michael G. Gardiner, George A. Koutsantonis, Colin L. Raston, Nicholas K. Roberts

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Abstract

Treatment of LiAlH₄/OEt₂ solutions with bulky trialkylphosphine hydrochloride salts or phosphine and then ethereal HCl yields thermally stable phosphine-alane adducts, viz. [H₃Al·P(C₆H₁₁)₃] (10), (H₃Al)_n·(PPr¹₂CH₂)₂ (n = 1 (11), 2 (12)), and [(H₃Al)₂·{P(C₆H₁₁)₂CH₂}₂] (13), which have been shown to be four-coordinate (10 and 13, Al-P = 2.467 (1), 2.460 (2) Å) or polymeric (13) with trigonal-bipyramidal aluminum centers (P apical) with exceptionally long Al-P bonds (2.732 Å (mean)). Ab initio calculations on the model species H₃Al·PH₃ (Al-P = 2.605 Å) give a stabilization energy of 13.2 kcal/mol relative to AlH₃ and PH₃, and dimerization to dialane, H₂Al(μ-H)₂AlH₂, and PH₃ is favored by 5.84 kcal/mol.

Original language	English
Pages (from-to)	1457-1459
Number of pages	3
Journal	Organometallics
Volume	11
Issue number	4
DOIs	https://doi.org/10.1021/om00040a013
Publication status	Published - 1 Apr 1992
Externally published	Yes

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title = "Stable Tertiary Phosphine Adducts of Alane",

abstract = "Treatment of LiAlH4/OEt2 solutions with bulky trialkylphosphine hydrochloride salts or phosphine and then ethereal HCl yields thermally stable phosphine-alane adducts, viz. [H3Al·P(C6H11)3] (10), (H3Al)n·(PPr12CH2)2 (n = 1 (11), 2 (12)), and [(H3Al)2·{P(C6H11)2CH2}2] (13), which have been shown to be four-coordinate (10 and 13, Al-P = 2.467 (1), 2.460 (2) {\AA}) or polymeric (13) with trigonal-bipyramidal aluminum centers (P apical) with exceptionally long Al-P bonds (2.732 {\AA} (mean)). Ab initio calculations on the model species H3Al·PH3 (Al-P = 2.605 {\AA}) give a stabilization energy of 13.2 kcal/mol relative to AlH3 and PH3, and dimerization to dialane, H2Al(μ-H)2AlH2, and PH3 is favored by 5.84 kcal/mol.",

author = "Bennett, {Frederick R.} and Elms, {Fiona M.} and Gardiner, {Michael G.} and Koutsantonis, {George A.} and Raston, {Colin L.} and Roberts, {Nicholas K.}",

year = "1992",

month = apr,

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doi = "10.1021/om00040a013",

language = "English",

volume = "11",

pages = "1457--1459",

journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Stable Tertiary Phosphine Adducts of Alane

AU - Bennett, Frederick R.

AU - Elms, Fiona M.

AU - Gardiner, Michael G.

AU - Koutsantonis, George A.

AU - Raston, Colin L.

AU - Roberts, Nicholas K.

PY - 1992/4/1

Y1 - 1992/4/1

N2 - Treatment of LiAlH4/OEt2 solutions with bulky trialkylphosphine hydrochloride salts or phosphine and then ethereal HCl yields thermally stable phosphine-alane adducts, viz. [H3Al·P(C6H11)3] (10), (H3Al)n·(PPr12CH2)2 (n = 1 (11), 2 (12)), and [(H3Al)2·{P(C6H11)2CH2}2] (13), which have been shown to be four-coordinate (10 and 13, Al-P = 2.467 (1), 2.460 (2) Å) or polymeric (13) with trigonal-bipyramidal aluminum centers (P apical) with exceptionally long Al-P bonds (2.732 Å (mean)). Ab initio calculations on the model species H3Al·PH3 (Al-P = 2.605 Å) give a stabilization energy of 13.2 kcal/mol relative to AlH3 and PH3, and dimerization to dialane, H2Al(μ-H)2AlH2, and PH3 is favored by 5.84 kcal/mol.

AB - Treatment of LiAlH4/OEt2 solutions with bulky trialkylphosphine hydrochloride salts or phosphine and then ethereal HCl yields thermally stable phosphine-alane adducts, viz. [H3Al·P(C6H11)3] (10), (H3Al)n·(PPr12CH2)2 (n = 1 (11), 2 (12)), and [(H3Al)2·{P(C6H11)2CH2}2] (13), which have been shown to be four-coordinate (10 and 13, Al-P = 2.467 (1), 2.460 (2) Å) or polymeric (13) with trigonal-bipyramidal aluminum centers (P apical) with exceptionally long Al-P bonds (2.732 Å (mean)). Ab initio calculations on the model species H3Al·PH3 (Al-P = 2.605 Å) give a stabilization energy of 13.2 kcal/mol relative to AlH3 and PH3, and dimerization to dialane, H2Al(μ-H)2AlH2, and PH3 is favored by 5.84 kcal/mol.

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DO - 10.1021/om00040a013

M3 - Article

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SN - 0276-7333

VL - 11

SP - 1457

EP - 1459

JO - Organometallics

JF - Organometallics

IS - 4

ER -

Stable Tertiary Phosphine Adducts of Alane

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