Donor-acceptor interactions with electrophilic terminal phosphinidene complexes

Grigoleit S, Alijah A, Rozhenko AB, Streubel R, Schoeller W (2002)
JOURNAL OF ORGANOMETALLIC CHEMISTRY 643-644: 223-230.

Journal Article | Published | English

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Abstract
Donor-acceptor interactions of Lewis bases, such as amine, phosphine, cyanic acid and phosphaalkine with various phosphinidene complexes carrying a W(CO)(5) fragment are studied by means of density functional calculations. Accordingly, the donor interactions can be divided into two categories. In terms of energy an amine binds stronger than a phosphine to a phosphinidene. the resulting Do-P bond is longer (N-P) or equal (P-P) with respect to a corresponding single bond, This tendency is also revealed in the corresponding transition metal complexes. In all cases the singlet-triplet energy separation values of the resulting donor-adducts are fairly small. A donor with a pi-system, such as HCN yields a shorter N-P bond, but the resulting donor-adduct is even less stable with respect to decomposition into a singlet PH complex and cyanic acid. Similar considerations with HCP reveal only a weak donor addition of this fragment to the parent PH complex but a facile rearrangement of the adduct to the diphosphirene transition metal complex. The diaminophosphino-PH possesses a singlet ground state, its corresponding transition metal complex reveals a fairly small singlet-triplet energy separation. It can be considered as a nucleophilic PH complex in contrast to the other homologues which reveal an electrophilic behaviour. (C) 2002 Published by Elsevier Science B.V.
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Grigoleit S, Alijah A, Rozhenko AB, Streubel R, Schoeller W. Donor-acceptor interactions with electrophilic terminal phosphinidene complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 2002;643-644:223-230.
Grigoleit, S., Alijah, A., Rozhenko, A. B., Streubel, R., & Schoeller, W. (2002). Donor-acceptor interactions with electrophilic terminal phosphinidene complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 643-644, 223-230.
Grigoleit, S., Alijah, A., Rozhenko, A. B., Streubel, R., and Schoeller, W. (2002). Donor-acceptor interactions with electrophilic terminal phosphinidene complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY 643-644, 223-230.
Grigoleit, S., et al., 2002. Donor-acceptor interactions with electrophilic terminal phosphinidene complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 643-644, p 223-230.
S. Grigoleit, et al., “Donor-acceptor interactions with electrophilic terminal phosphinidene complexes”, JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 643-644, 2002, pp. 223-230.
Grigoleit, S., Alijah, A., Rozhenko, A.B., Streubel, R., Schoeller, W.: Donor-acceptor interactions with electrophilic terminal phosphinidene complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 643-644, 223-230 (2002).
Grigoleit, S, Alijah, A, Rozhenko, AB, Streubel, R, and Schoeller, Wolfgang. “Donor-acceptor interactions with electrophilic terminal phosphinidene complexes”. JOURNAL OF ORGANOMETALLIC CHEMISTRY 643-644 (2002): 223-230.
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