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 H.
AU - Witt, Eva
N1 - Publisher Copyright:
© WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 1998.
PY - 2008/1/1
Y1 - 2008/1/1
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 ShCU/LiCioHs (GeCl2-dioxane and SnCl2) with LiC(PMe2)2(SiMe3), 1, and LiC(PMe2)3 (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+BPh4- was obtained by reaction of the triphosphete, 6, and (Cl)(Ph2)P=C(PPh2)(SiMe3), 7, with NaBPh4. The cation adopts a similiar ψ-tbp geometry as the E(II) compounds (E = Si, Ge, Sn), but differences are also important.
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 ShCU/LiCioHs (GeCl2-dioxane and SnCl2) with LiC(PMe2)2(SiMe3), 1, and LiC(PMe2)3 (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+BPh4- was obtained by reaction of the triphosphete, 6, and (Cl)(Ph2)P=C(PPh2)(SiMe3), 7, with NaBPh4. The cation adopts a similiar ψ-tbp geometry as the E(II) compounds (E = Si, Ge, Sn), but differences are also important.
KW - Phosphinomethanides
KW - Phosphorus cation(P)
KW - Spirocyclic E compounds
UR - http://www.scopus.com/inward/record.url?scp=85214761127&partnerID=8YFLogxK
U2 - 10.1002/9783527619900.ch11
DO - 10.1002/9783527619900.ch11
M3 - Chapter
AN - SCOPUS:85214761127
SN - 9783527620746
SP - 65
EP - 69
BT - Organosilicon Chemistry III
PB - wiley
ER -