title: 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.
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.
authors.affiliation: Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy.
authors.forename: Elisabetta
authors.initials: E
authors.lastname: Guidoboni
authors.forename: Isaac
authors.initials: I
authors.lastname: de los Rios
authors.forename: Andrea
authors.initials: A
authors.lastname: Ienco
authors.forename: Lorenza
authors.initials: L
authors.lastname: Marvelli
authors.forename: Carlo
authors.initials: C
authors.lastname: Mealli
authors.forename: Antonio
authors.initials: A
authors.lastname: Romerosa
authors.forename: Roberto
authors.initials: R
authors.lastname: Rossi
authors.forename: Maurizio
authors.initials: M
authors.lastname: Peruzzini