Unprecedented eta(1)-P(basal) coordination of P(4)X(3) molecules (X = S, Se). An experimental and theoretical study of the apical vs basal complexation dichotomy

Elisabetta Guidoboni; Isaac de los Rios; Andrea Ienco; Lorenza Marvelli; Carlo Mealli; Antonio Romerosa; Roberto Rossi; Maurizio Peruzzini

doi:10.1021/ic010559f

Unprecedented eta(1)-P(basal) coordination of P(4)X(3) molecules (X = S, Se). An experimental and theoretical study of the apical vs basal complexation dichotomy

Inorg Chem. 2002 Feb 25;41(4):659-68. doi: 10.1021/ic010559f.

Authors

Elisabetta Guidoboni¹, Isaac de los Rios, Andrea Ienco, Lorenza Marvelli, Carlo Mealli, Antonio Romerosa, Roberto Rossi, Maurizio Peruzzini

Affiliation

¹ Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy.

PMID: 11849064
DOI: 10.1021/ic010559f

Abstract

Reaction of [(triphos)Re(CO)(2)(OTf)] (1) [triphos = MeC(CH(2)PPh(2))(3); OTf = OSO(2)CF(3)] with P(4)S(3) and P(4)Se(3) yields pairs of coordination isomers, namely, [(triphos)Re(CO)(2)[eta(1)-P(apical)-P(4)X(3)]](+) (X = S, 2; Se, 5) and [(triphos)Re(CO)(2)[eta(1)-P(basal)-P(4)X(3)]](+) (X = S, 3; Se, 6). The latter represent the first examples of the eta(1)-P(basal) coordination achieved by the P(4)X(3) molecular cage. Further reaction of 2/3 and 5/6 mixtures with 1 affords the dinuclear species [[(triphos)Re(CO)(2)](2)[mu,eta(1:1)-P(apical,)P(basal)-P(4)X(3)]](2+) (X = S, 4; Se, 7) in which the unprecedented M-eta(1)-P(basal)/eta(1)-P(apical)-M' bridging coordination of the P(4)X(3) molecule is accomplished. A theoretical analysis of the bonding properties of the two coordination isomers is also presented. The directionality of apical vs basal phosphorus lone pairs is also discussed in terms of MO arguments.