Reactions of Sn(NMe2)2 with Alkali-Metal tert-Butylphosphides tBuPHM (M = Li, Na, K): Evidence for Metal-Induced Modification of the Tin(II) P
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- 作者：Felipe Garcí ; a ; Jö ; rg P. Hehn ; Richard A. Kowenicki ; Mary McPartlin ; Christopher M. Pask ; Alexander Rothenberger ; Matthew L. Stead ; and Dominic S. Wright
- 刊名：Organometallics
- 出版年：2006
- 出版时间：June 19, 2006
- 年：2006
- 卷：25
- 期：13
- 页码：3275 - 3281
- 全文大小：185K
- 年卷期：v.25,no.13(June 19, 2006)
- ISSN：1520-6041
文摘
The 1:2 or 1:3 stoichiometric reactions of Sn(NMe2)2 with tBuPHM (M = Li, Na, K) in THF give theheterometallic alkali-metal/Sn(II) phosphinidene cages [{Sn2(PtBu)3}2Li4·4THF] (1), [{Sn3(PtBu)4}Na·3THF]-[Na(THF)6]+ (2), [{Sn3(PtBu)4}2(K·THF)3]-[K(THF)6]+ (4), and [{Sn4(PtBu)5}K2·5THF] (5) (THF =C4H8O). The 2:3 
3:4 4:5 numerical progression observed in the Sn(II):PtBu ratios of the[{Sn2(PtBu)3}2]4-, [{Sn3(PtBu)4}]2-, and [{Sn4(PtBu)5}]2- anions of these complexes is dependent onthe alkali-metal countercations present. The fact that the Lewis base donor has no effect on theresulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex[{Sn3(PtBu)4}Na2·2PMDETA·THF] (3) (PMDETA = (Me2NCH2CH2)2NMe) in the 1:2 reaction ofSn(NMe2)2 with tBuPHNa in the presence of PMDETA (containing the same [{Sn3(PtBu)4}]2- dianionas found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relationto those of the previously reported complex 1.
3:4 4:5 numerical progression observed in the Sn(II):PtBu ratios of the[{Sn2(PtBu)3}2]4-, [{Sn3(PtBu)4}]2-, and [{Sn4(PtBu)5}]2- anions of these complexes is dependent onthe alkali-metal countercations present. The fact that the Lewis base donor has no effect on theresulting Sn(II) phosphinidene anions is indicated by the formation of the PMDETA-solvated complex[{Sn3(PtBu)4}Na2·2PMDETA·THF] (3) (PMDETA = (Me2NCH2CH2)2NMe) in the 1:2 reaction ofSn(NMe2)2 with tBuPHNa in the presence of PMDETA (containing the same [{Sn3(PtBu)4}]2- dianionas found in 2). The syntheses and X-ray structures of the new complexes 2-5 are discussed in relationto those of the previously reported complex 1.