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Alvarez P, García F, Hehn JP, et al. Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb). Chemistry. 2007;13(4):1078-89doi: 10.1002/chem.200600633.
Alvarez, P., García, F., Hehn, J. P., Kraus, F., Lawson, G. T., Korber, N., Mosquera, M. E., McPartlin, M., Moncrieff, D., Pask, C. M., Woods, A. D., & Wright, D. S. (2007). Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb). Chemistry (Weinheim an der Bergstrasse, Germany), 13(4), 1078-89. https://doi.org/10.1002/chem.200600633
Alvarez, Paula, et al. "Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb)." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 13,4 (2007): 1078-89. doi: https://doi.org/10.1002/chem.200600633
Alvarez P, García F, Hehn JP, Kraus F, Lawson GT, Korber N, Mosquera ME, McPartlin M, Moncrieff D, Pask CM, Woods AD, Wright DS. Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb). Chemistry. 2007;13(4):1078-89. doi: 10.1002/chem.200600633. PMID: 17086565.
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Chemistry. 2007;13(4):1078-89. doi: 10.1002/chem.200600633.

Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb).

Chemistry (Weinheim an der Bergstrasse, Germany)

Paula Alvarez, Felipe García, Jörg P Hehn, Florian Kraus, Gavin T Lawson, Nikolaus Korber, Marta E G Mosquera, Mary McPartlin, David Moncrieff, Christopher M Pask, Anthony D Woods, Dominic S Wright

Affiliations

  1. Chemistry Department, Cambridge University, Lensfield Road, Cambridge CB2 1EW, UK.

PMID: 17086565 DOI: 10.1002/chem.200600633

Abstract

The reactions of the SnII base Sn(NMe2)2 with CyPHM (Cy=cyclohexyl) produce a range of products, depending primarily on the alkali metal (M) involved. The 1:3 stoichiometric reaction of Sn(NMe2)2 with CyPHNa in the presence of the Lewis base donor PMDETA (PMDETA=(Me2NCH2CH2)2NMe) gives [(NaPMDETA)2{Sn(mu-PCy)}3] (3), containing the electron-deficient [{Sn(mu-PCy)}3]2- dianion. Natural bond order (NBO) and electron localisation function (ELF) calculations show that this species is described most appropriately by a two-electron, three-centre Sn3 bonding model. Evidence that 3 results from phosphide coupling is provided by the 1:1 reaction of Sn(NMe2)2 with CyPHNa in the presence of PMDETA, which gives 3 and trace amounts of (NaPMDETA)2[{Sn(mu-PCy)}2(mu-PCyPCy)] (4) (containing one PCyPCy2- dianion). Greater extents of phosphide coupling are observed as the size of the Group 1 metal is increased. Thus, the 1:3 reaction of Sn(NMe2)2 with CyPHK in THF gives the co-crystalline product {(K2 THF)2[{Sn(mu-PCyPCy)}2(mu-PCy)]}0.9{(K2 THF)2[{Sn(mu-PCy)}2(mu-PCyPCy)]}0.1 (5) (containing [{Sn(mu-PCyPCy)}2(mu-PCy)]2- and [{Sn(mu-PCy)}2(mu-PCyPCy)]2- dianions), whereas the analogous reaction of Sn(NMe2)2 with RbPHCy gives [RbPMDETA{(CyP)3SnP(H)Cy}] (6) (containing a cyclic {(CyP)3Sn} unit).

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