(Ph₃P)₂Rh(SPCy₂): A complex containing a side-on bonded η²-secondary phosphine sulfide anion

Abstract

L u c~o GELMINI and DOUGLAS W. STEPHAN. Can. J. Chem. 66, 2647. The reaction of Cp2Zr(SPCy2)2 with either (Ph3P)3RhH(CO) or (Ph3P)4RhH led not to the expected heterobimetallic species but rather to a novel Rh species (Ph3P)2Rh(SPCy2), 4. The 3 '~{ '~} NMR spectrum of this complex is an ABCX pattern. The molecular geometry of 4 was confirmed by a crystallographic study. Compound 4 cry~tallizes in the space group P 2 { / c with a = 10.912(1)A, b = 12.335(2) A, c = 32.346(7) A, P = 96.17(1)", V = 4328(1) A3, and Z = 4. The coordination sphere about Rh in 4 is pseudo-square planar, containing three phosphorus and a sulfur atom from the two coordinated phosphines and a side-on bonded SPCy2 moiety. This structural study confirms that the secondary phosphine chalcogenide is bonded to Rh in an -q2 fashion. The complex 4 is only the fourth example in which this mode of binding has been crystallographically confirmed and is the first such species to involve one of the Pt group metals.Lucro GELMINI et DOUGLAS W. STEPHAN. Can. J. Chem. 66,2647. La rkaction du Cp2Zr(SPCy2)2 avec soit le (Ph3P)3RhH(CO) ou le (Ph3P)4RhH ne conduit pas aux especes hCtCrobimCtalliques attendues mais plut8t i une nouvelle espece de Rh, le (Ph3P) [Traduit par la revue] Introduction Our interest in early/late heterobimetallics (1-12) has led us to investigate the use of functionalized early transition metal complexes as metalloligands for later transition metals. In a recent paper we described syntheses, structures and chemistry of some Ti, Zr, and Hf complexes of secondary phosphine sulfides and selenides (9). In these Ti, Zr, and Hf complexes, bonding of XPR2 anions through chalcogenide was observed. However, secondary phosphine chalcogenides or their conjugate bases are known to exhibit at least six different bonding modes (Fig. 1) (13-35). One of these modes involves bonding in which the chalcogen and phosphorus nuclei are bound to different metal atoms (Fig. l(e)); however, this type of ligand system has not been employed to synthesize mixed metal species. Thus, the complex C~~z r ( S P c y~)~, 1, seemed a suitable synthon for the preparation of Zr/M heterobimetallics. In this paper, we describe some initial investigations that show that reactions of 1 with two Rh-hydride species result in the cleavage of the Zr-S bond, yielding the monometallic species (Ph3P)2Rh(SPCy2), 4. The species, 4, has been characterized crystallographically. The results show that the secondary phosphine sulfide moiety is side-on bonded in an r12 fashion. Although this form of binding is known, this report is only the fourth in which this form of bonding has been structurally confirmed. Experimental sectionAll preparations were done under an atmosphere of dry, 02-free N. . Solvents were reagent grade, distilled from the appropriate drying agents under N2, and degassed by the freeze-thaw method at least three times prior to use. 3 1~{ 1~} NMR spectra were recorded on a Bruker AC-200 spectrometer, using external 85% H3PO4 as the 'present address:

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

“…The Pb–S1, P–S1, and PS2 bond distances are 2.6370(13), 2.0528(17), and 1.9755(18) Å, respectively. The latter bond length is similar to those in other compounds with PS double bonds . The Pb···S2 distance (3.276 Å) is smaller than the sum of the van der Waals radii (3.82 Å), suggesting that there may be weak interaction.…”

“…The latter bond length is similar to those in other compounds with PS double bonds. 36 The Pb•••S2 distance (3.276 Å) is smaller than the sum of the van der Waals radii (3.82 Å), 29 suggesting that there may be weak interaction. The 31 P{ 1 H} NMR spectrum of 4-Pb-Cy-S 2 shows a single resonance at δ P 84.6 ppm, with lead satellites ( 2 J PPb = 189 Hz).…”