Reactions of Sn(NMe2)2 with alkali-metal tert-butylphosphidestBuPHM (M = Li, Na, K): Evidence for metal-induced modification of the tin(II) phosphinidene anions

Felipe García; Jörg P. Hehn; Richard A. Kowenicki; Mary McPartlin; Christopher M. Pask; Alexander Rothenberger; Matthew L. Stead; Dominic S. Wright

doi:10.1021/om060167m

Reactions of Sn(NMe₂)₂ with alkali-metal tert-butylphosphides^tBuPHM (M = Li, Na, K): Evidence for metal-induced modification of the tin(II) phosphinidene anions

Felipe García, Jörg P. Hehn, Richard A. Kowenicki, Mary McPartlin, Christopher M. Pask, Alexander Rothenberger, Matthew L. Stead, Dominic S. Wright^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

The 1:2 or 1:3 stoichiometric reactions of Sn(NMe₂)₂ with ^tBuPHM (M = Li, Na, K) in THF give the heterometallic alkali-metal/Sn(II) phosphinidene cages [{Sn₂(P^tBu) ₃}₂Li₄·4THF] (1), [{Sn ₃(F^tBu)₄}Na·3THF]^--[Na(THF) ₆]⁺ (2), [{Sn₃(F^tBu) ₄}₂(K·THF)₃]^-[K(THF) ₆]⁺ (4), and [{Sn₄(F^tBu)5}K ₂·5THF] (5) (THF = C₄H₈O). The 2:3 → 3:4 → 4:5 numerical progression observed in the Sn(II):P ^tBu ratios of the [{Sn₂(F^tBu)₃} ₂]^4-, [{Sn₃(F^tBu)₄}] _2-, and [{Sn₄(F^tBu)₅}]_2- anions of these complexes is dependent on the alkali-metal countercations present. The fact that the Lewis base donor has no effect on the resulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex [{Sn₃(F^tBu)₄}Na₂⋯ 2PMDETA-THF] (3) (PMDETA = (Me₂NCH₂CH₂) ₂NMe) in the 1:2 reaction of Sn(NMe₂)₂ with ^tBuPHNa in the presence of PMDETA (containing the same [{Sn ₃(F^tBu)4}]^2- dianion as found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relation to those of the previously reported complex 1.

Original language	English (US)
Pages (from-to)	3275-3281
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	13
DOIs	https://doi.org/10.1021/om060167m
State	Published - Jun 19 2006
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{55c7bf4f12314960b7d31fd86b234a2a,

title = "Reactions of Sn(NMe2)2 with alkali-metal tert-butylphosphidestBuPHM (M = Li, Na, K): Evidence for metal-induced modification of the tin(II) phosphinidene anions",

abstract = "The 1:2 or 1:3 stoichiometric reactions of Sn(NMe2)2 with tBuPHM (M = Li, Na, K) in THF give the heterometallic alkali-metal/Sn(II) phosphinidene cages [{Sn2(PtBu) 3}2Li4·4THF] (1), [{Sn 3(FtBu)4}Na·3THF]--[Na(THF) 6]+ (2), [{Sn3(FtBu) 4}2(K·THF)3]-[K(THF) 6]+ (4), and [{Sn4(FtBu)5}K 2·5THF] (5) (THF = C4H8O). The 2:3 → 3:4 → 4:5 numerical progression observed in the Sn(II):P tBu ratios of the [{Sn2(FtBu)3} 2]4-, [{Sn3(FtBu)4}] 2-, and [{Sn4(FtBu)5}]2- anions of these complexes is dependent on the alkali-metal countercations present. The fact that the Lewis base donor has no effect on the resulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex [{Sn3(FtBu)4}Na2⋯ 2PMDETA-THF] (3) (PMDETA = (Me2NCH2CH2) 2NMe) in the 1:2 reaction of Sn(NMe2)2 with tBuPHNa in the presence of PMDETA (containing the same [{Sn 3(FtBu)4}]2- dianion as found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relation to those of the previously reported complex 1.",

author = "Felipe Garc{\'i}a and Hehn, {J{\"o}rg P.} and Kowenicki, {Richard A.} and Mary McPartlin and Pask, {Christopher M.} and Alexander Rothenberger and Stead, {Matthew L.} and Wright, {Dominic S.}",

year = "2006",

month = jun,

day = "19",

doi = "10.1021/om060167m",

language = "English (US)",

volume = "25",

pages = "3275--3281",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Reactions of Sn(NMe2)2 with alkali-metal tert-butylphosphidestBuPHM (M = Li, Na, K)

T2 - Evidence for metal-induced modification of the tin(II) phosphinidene anions

AU - García, Felipe

AU - Hehn, Jörg P.

AU - Kowenicki, Richard A.

AU - McPartlin, Mary

AU - Pask, Christopher M.

AU - Rothenberger, Alexander

AU - Stead, Matthew L.

AU - Wright, Dominic S.

PY - 2006/6/19

Y1 - 2006/6/19

N2 - The 1:2 or 1:3 stoichiometric reactions of Sn(NMe2)2 with tBuPHM (M = Li, Na, K) in THF give the heterometallic alkali-metal/Sn(II) phosphinidene cages [{Sn2(PtBu) 3}2Li4·4THF] (1), [{Sn 3(FtBu)4}Na·3THF]--[Na(THF) 6]+ (2), [{Sn3(FtBu) 4}2(K·THF)3]-[K(THF) 6]+ (4), and [{Sn4(FtBu)5}K 2·5THF] (5) (THF = C4H8O). The 2:3 → 3:4 → 4:5 numerical progression observed in the Sn(II):P tBu ratios of the [{Sn2(FtBu)3} 2]4-, [{Sn3(FtBu)4}] 2-, and [{Sn4(FtBu)5}]2- anions of these complexes is dependent on the alkali-metal countercations present. The fact that the Lewis base donor has no effect on the resulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex [{Sn3(FtBu)4}Na2⋯ 2PMDETA-THF] (3) (PMDETA = (Me2NCH2CH2) 2NMe) in the 1:2 reaction of Sn(NMe2)2 with tBuPHNa in the presence of PMDETA (containing the same [{Sn 3(FtBu)4}]2- dianion as found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relation to those of the previously reported complex 1.

AB - The 1:2 or 1:3 stoichiometric reactions of Sn(NMe2)2 with tBuPHM (M = Li, Na, K) in THF give the heterometallic alkali-metal/Sn(II) phosphinidene cages [{Sn2(PtBu) 3}2Li4·4THF] (1), [{Sn 3(FtBu)4}Na·3THF]--[Na(THF) 6]+ (2), [{Sn3(FtBu) 4}2(K·THF)3]-[K(THF) 6]+ (4), and [{Sn4(FtBu)5}K 2·5THF] (5) (THF = C4H8O). The 2:3 → 3:4 → 4:5 numerical progression observed in the Sn(II):P tBu ratios of the [{Sn2(FtBu)3} 2]4-, [{Sn3(FtBu)4}] 2-, and [{Sn4(FtBu)5}]2- anions of these complexes is dependent on the alkali-metal countercations present. The fact that the Lewis base donor has no effect on the resulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex [{Sn3(FtBu)4}Na2⋯ 2PMDETA-THF] (3) (PMDETA = (Me2NCH2CH2) 2NMe) in the 1:2 reaction of Sn(NMe2)2 with tBuPHNa in the presence of PMDETA (containing the same [{Sn 3(FtBu)4}]2- dianion as found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relation to those of the previously reported complex 1.

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U2 - 10.1021/om060167m

DO - 10.1021/om060167m

M3 - Article

AN - SCOPUS:33745751395

SN - 0276-7333

VL - 25

SP - 3275

EP - 3281

JO - Organometallics

JF - Organometallics

IS - 13

ER -

Reactions of Sn(NMe₂)₂ with alkali-metal tert-butylphosphides^tBuPHM (M = Li, Na, K): Evidence for metal-induced modification of the tin(II) phosphinidene anions

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