Abstract

The fulvene complex (?6-C5Me4CH 2)Re(C6F5)(CO)2 reacts at the exocyclic methylene carbon with potassium diphenylphosphide to yield the anionic species [(?5-C5Me4CH2PPh 2)Re(C6F5)(CO)2]- (1). Protonation of 1 with HCl at 0 °C produces the hydride complex trans-(?5-C5Me4CH2PPh 2)Re(C6F5)(H)(CO)2 (2). Thermolysis of a hexanes solution of 2, under nitrogen atmosphere, produces the chelated complex (?5:?1-C5Me4CH 2PPh2)Re(CO)2 (3) in good yield. The thermolysis under a CO atmosphere affords a mixture of the complexes (?5:?1-C5Me4CH 2PPh2)Re(CO)2 (3) and (?5-C 5Me4CH2PPh2)Re(CO)3 (4a). The reaction of 3 with two electron donor ligands yields (?5- C5Me4CH2PPh2)Re(CO)2(L) (4a, L = CO; 4b, L = PMe3; 4c, L = tBuNC). Complex 3 also reacts with I2, HBF4 and MeOTf to yield the cationic compounds trans-[(?5:?1-C5Me 4CH2PPh2)Re(R)(CO)2]+ (5a, R = I; 5b, R = H; 5c, R = Me). Upon treatment with chloroform, the hydride complex 5b converts to the corresponding chloro derivative 5d. The trans stereochemistry for complexes 5 have been assigned on basis of ?(CO) IR intensities and 13C-NMR chemical shifts. The reaction of the cationic complexes (5a, 5c) with KI and Me3NO·2H2O yields the neutral species cis-(?5:?1-C 5Me4CH2PPh2)Re(I)(R)(CO) (6a, R = I, 6b, R = Me). The molecular structure of 3 and 6a have been determined by X-ray crystallography. © 2009 The Royal Society of Chemistry.