TY - CHAP
T1 - Isoelectronic Replacement of Si by P+
T2 - A Comparative Study of the Structures of the Spiro-Cyclic EII Compounds E[C(PMe2)2(X)]2 (E = Si, Ge, Sn; X = PMe2, SiMe3) and a Novel Spirocyclic 10 e-Phosphorus Cation (PIII) P[C(PPh2)2(SiMe3)]2+
AU - Karsch, Hans Heinz
AU - Witt, Eva
N1 - Publisher Copyright:
© 2008 VCH Verlagsgesellschaft mbH. All rights reserved.
PY - 2008/6/10
Y1 - 2008/6/10
N2 - The synthesis of stable group 14 compounds E[(Me2P)2CX]2(E = Si, Ge, Sn; X = PMe2, SiMe3) in the formal oxidation state + 2 is achieved by reacting Si2Cl6iC10H8 (GeCl2dioxane and SnC12) with LiC(PMe2)2Me3), 1, and LiC(PMe& (3) respectively. An X-ray structure analysis of Si[(Me2P)2C(SiMe3)]2(2) Ge[(Me2P)3C]2 (4b) Sn[(Me2P)2C(SiMe3)]2 (5a) and Sn[(Me2P)3C]2 (5b) shows, that in the crystal, 2, 4b, 5a,b, have a distorted pseudo-trigonal-bipyramidal(Ψ-tbp) structure, in which E (E = Si, Ge, Sn) as a spiro center, is surrounded by four phosphorus atoms. A common feature of the four compounds is also the marked difference between axial and equatorial element-phosphorus bond lengths. An analogous P' compound P[(Ph2P)2C(SiMe3)]2+BPb4- was obtained by reaction of the triphosphete, 6, and (CI)(Ph2)P2=C(PPh2)(SiMe3), 7, with NaBPb.
AB - The synthesis of stable group 14 compounds E[(Me2P)2CX]2(E = Si, Ge, Sn; X = PMe2, SiMe3) in the formal oxidation state + 2 is achieved by reacting Si2Cl6iC10H8 (GeCl2dioxane and SnC12) with LiC(PMe2)2Me3), 1, and LiC(PMe& (3) respectively. An X-ray structure analysis of Si[(Me2P)2C(SiMe3)]2(2) Ge[(Me2P)3C]2 (4b) Sn[(Me2P)2C(SiMe3)]2 (5a) and Sn[(Me2P)3C]2 (5b) shows, that in the crystal, 2, 4b, 5a,b, have a distorted pseudo-trigonal-bipyramidal(Ψ-tbp) structure, in which E (E = Si, Ge, Sn) as a spiro center, is surrounded by four phosphorus atoms. A common feature of the four compounds is also the marked difference between axial and equatorial element-phosphorus bond lengths. An analogous P' compound P[(Ph2P)2C(SiMe3)]2+BPb4- was obtained by reaction of the triphosphete, 6, and (CI)(Ph2)P2=C(PPh2)(SiMe3), 7, with NaBPb.
KW - Phosphinomethanides
KW - Phosphorus cation(PIII)
KW - Spirocyclic EII compounds
UR - http://www.scopus.com/inward/record.url?scp=84959167363&partnerID=8YFLogxK
U2 - 10.1002/9783527620777.ch11b
DO - 10.1002/9783527620777.ch11b
M3 - Chapter
AN - SCOPUS:84959167363
SN - 9783527323470
SP - 65
EP - 69
BT - Organosilicon Chemistry Set
PB - wiley
ER -