The reactions of Ir(CO)Cl(PPh3)2 with HSnPh3

A reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has the H and SnPh3 ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh3 by a Cl for H ligand exchange to yield the new compound H2Ir(CO)(SnPh3)(PPh3)2, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh3 to replace the Cl ligand with SnPh3 and one of the PPh3 ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands.

Graphical abstractA reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has a cis-stereochemistry of the H and SnPh3 ligands. Compound 2 reacts with HSnPh3 by a Cl for H ligand exchange to yield the dihydride complex H2Ir(CO)(SnPh3)(PPh3)2, 3. Under CO, 1 reacts with HSnPh3 to yield the complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 to yield the HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands. Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The reactions of Ir(CO)Cl(PPh3)2 with HSnPh3 have been examined in presence and absence of CO. ► Oxidative-addition with cis-stereochemistry was observed in the absence of CO. ► In the presence of CO, the carbonyl compounds Ir(CO)3(SnPh3)(PPh3) and HIr(CO)2(SnPh3)2(PPh3) were obtained by one and two addition of HSnPh3.