Acceptor pincer Ru(ii) chemistryCCDC 886418-886427. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt31234d

A series of new acceptor pincer Ru( ii ) complexes are reported. The carbonyl complex ( CF 3 PCP)Ru(CO)Cl 2 − Et 3 NH + is obtained from the reaction of CF 3 PCPH with [(cod)Ru(μ-Cl) 2 ] n . Chloride displacement with CF 3 PCPH, CO, PPh 3 , or C 2 H 4 gave complexes of the type ( CF 3 PCP)Ru(CO)(L)Cl, or in the case of CF 3 PCPH, the bridged dimeric complex [( CF 3 PCP)Ru(CO)Cl] 2 (μ- CF 3 PCPH). Chloride abstraction from ( CF 3 PCP)Ru(CO)(L)Cl, L = CO or PPh 3 by (Et 3 Si) 2 (μ-H) + B(C 6 F 5 ) 4 − followed by Et 3 N addition produced ( CF 3 PCP)Ru(CO)(L)(H) products. Reaction of cis -( CF 3 PCP)Ru(CO) 2 Cl with (Et 3 Si) 2 (μ-H) + B(C 6 F 5 ) 4 − in the presence of excess CO afforded ( CF 3 PCP)Ru(CO) 3 + . The reaction of CF 3 PCPH with (PPh 3 ) 3 Ru(H)(O 2 CR) (R = Me or Ph) produced the corresponding carboxylate complexes ( CF 3 PCP)Ru(PPh 3 )(O 2 CR). ( CF 3 PCP)Ru(CO)Cl 2 − Et 3 NH + serves as a convenient precursor for Cl − displacement products ( CF 3 PCP)Ru(CO)(L)Cl (L = 1/2 CF 3 PCPH, CO, PPh 3 , or C 2 H 4 ), ( CF 3 PCP)Ru(CO)(L)(H) products (L = CO, Ph 3 P), and ( CF 3 PCP)Ru(CO) 3 + . The reaction of CF 3 PCPH with (PPh 3 ) 3 Ru(H)(O 2 CR) (R = Me or Ph) produces the corresponding carboxylate complexes ( CF 3 PCP)Ru(PPh 3 )(O 2 CR).