Organometallic Chemistry of the Difluorodithiophosphate Anion

Abstract

An improved synthetic route of [N n Pr 4 ][S 2 PF 2 ] was devised, and its structure was determined. This unusual dithiophosphate is a good ligand for low valent metal centers and examples of this being hydrolytically stable ruthenium complexes RuH(CO)(S 2 PF 2 )(PPh 3 ) 2 , RuCl(CO)(S 2 PF 2 )(PPh 3 ) 2 and Ru-(S 2 PF 2 ) 2 (PPh 3 ) 2 . Taken together these results give an insight into the bonding of the S 2 PF 2 anion to low oxidation state complexes. A comparison of the structural features and reactivity of the complexes with other known Ru(II) complexes is presented. Ru(S 2 PF 2 ) 2 (PPh 3 ) 2 was successfully carbonylated to give a complex with monohapto and dihapto S 2 PF 2 ligands, Ru(CO)(η 1 -S 2 PF 2 )(η 2 -S 2 PF 2 )(PPh 3 ) 2 confirming the lability of the fluorothiophosphate anion. Isomers of this latter complex have been structurally characterized with cis and trans PPh 3 .

Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d8 and d6 Complexes of [η2-S3PF]2–

“…This suggests similar s-character of the P–F bond in the S 5 P 2 F 2 , S 3 PF, and S 2 POF ligands, but slightly more s-character in S 2 (SMe)­PF. The related fluorothiophosphate S 2 PF 2 showed a remarkable increase in 1 J PF of 100–150 Hz upon coordination of the ligand to Ru­(II) . This behavior is not as pronounced for [S 3 PF] 2– of [S 5 P 2 F 2 ] 2– coordination.…”

“…Selected Bond Lengths and Bond Angles of [(Cymene)Ru(S 3 PF)] 2 PF of 100−150 Hz upon coordination of the ligand to Ru(II) 56. This behavior is not as pronounced for [S 3 PF] 2− of [S 5 P 2 F 2 ] 2− coordination.…”