TY - JOUR
T1 - Carbodiphosphorane C(PPh3)2 as a single and twofold lewis base with boranes
T2 - Synthesis, crystal structures and theoretical studies on [H3B{C(PPh3)2}] and [{(μ-H)H 4B2}{C(PPh3)2}]+
AU - Petz, Wolfgang
AU - Öxler, Florian
AU - Neumüller, Bernhard
AU - Tonner, Ralf
AU - Frenking, Gernot
PY - 2009
Y1 - 2009
N2 - The donor-acceptor complex [(H3B)[C(PPh3) 2}] (2) has been synthesized by treating B2H6 with C(PPh3J2 and its geometry determined by X-ray structure analysis. Treatment of 2 with DME yields the complex [[(H-H)H 4B2)(C(PPh3J2J][B2H 7] (4), which has also been isolated and structurally characterized. Compound 4 is the first complex of a carbodiphosphorane where the carbon donor atom binds with its two-electron lone pairs to two main-group Lewis acids larger than protons. This reaction is likely to occur via initial formation of [(H3B)2- [C(PPh3J2)] (6), which subsequently reacts with B2H6, with loss of a hydride, to yield 4. Quantum chemical calculations of 2, 4+ and 6 show that the carbon-boron bonds in these complexes are very strong, and analysis of the bonding situation using the EDA, NBO and AIM methods reveals typical bonding patterns between the divalent carbon(O) moieties and one or two Lewis acids. The carbon donor atom of the carbodiphosphorane moiety remains strongly negatively charged even in the cation 4+.
AB - The donor-acceptor complex [(H3B)[C(PPh3) 2}] (2) has been synthesized by treating B2H6 with C(PPh3J2 and its geometry determined by X-ray structure analysis. Treatment of 2 with DME yields the complex [[(H-H)H 4B2)(C(PPh3J2J][B2H 7] (4), which has also been isolated and structurally characterized. Compound 4 is the first complex of a carbodiphosphorane where the carbon donor atom binds with its two-electron lone pairs to two main-group Lewis acids larger than protons. This reaction is likely to occur via initial formation of [(H3B)2- [C(PPh3J2)] (6), which subsequently reacts with B2H6, with loss of a hydride, to yield 4. Quantum chemical calculations of 2, 4+ and 6 show that the carbon-boron bonds in these complexes are very strong, and analysis of the bonding situation using the EDA, NBO and AIM methods reveals typical bonding patterns between the divalent carbon(O) moieties and one or two Lewis acids. The carbon donor atom of the carbodiphosphorane moiety remains strongly negatively charged even in the cation 4+.
KW - Ab initio calculations
KW - Bond energy
KW - Boranes
KW - Density functional calculations
KW - Donor-acceptor systems
UR - http://www.scopus.com/inward/record.url?scp=70350162322&partnerID=8YFLogxK
U2 - 10.1002/ejic.200900691
DO - 10.1002/ejic.200900691
M3 - 文章
AN - SCOPUS:70350162322
SN - 1434-1948
SP - 4507
EP - 4517
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 29-30
ER -