TY - JOUR
T1 - Synthesis and characterization of terminal [Re(XCO)(CO)[sub]2(triphos)] (X=N, P)
T2 - isocyanate versus phosphaethynolate complexes
AU - Alidori, Simone
AU - Heift, Dominikus
AU - Santiso-Quinones, Gustavo
AU - Benkå, Zoltán
AU - Grützmacher, Hansjörg
AU - Caporali, Maria
AU - Gonsalvi, Luca
AU - Rossin, Andrea
AU - Peruzzini, Maurizio
N1 - Note: This work was supported by the ETH Zurich, COST Action and CNR.
PY - 2012/11/12
Y1 - 2012/11/12
N2 - The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)2(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)2(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)2(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the ReI and the NCO group. The phosphaethynolate complex [Re(P´ú¥C´ú¥O)(CO)2(triphos)] is best described as a metallaphosphaketene with a ReI-phosphorus bond of highly covalent character.
AB - The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)2(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)2(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)2(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the ReI and the NCO group. The phosphaethynolate complex [Re(P´ú¥C´ú¥O)(CO)2(triphos)] is best described as a metallaphosphaketene with a ReI-phosphorus bond of highly covalent character.
KW - Chemistry
U2 - 10.1002/chem.201202590
DO - 10.1002/chem.201202590
M3 - Article
SN - 0947-6539
VL - 18
SP - 14805
EP - 14811
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 46
ER -