Synthesis, Reactivity, and Crystal Structure of the η 2 ‐Thiocarbamoyl Palladium Complex [Pd(PPh 3 ) 2 (η 2 ‐SCNMe 2 )][PF 6 ]

The η 1 ‐thiocarbamoyl palladium complexes [Pd(PPh 3 )(η 1 ‐SCNMe 2 )(η 2 ‐S 2 R)] (R = P(OEt) 2 , 2 ; CNEt 2 , 3 ) and trans ‐[Pd(PPh 3 ) 2 (η 1 ‐SCNMe 2 )(η 1 ‐Spy)], 4 , (pyS: pyridine‐2‐thionate) are prepared by reacting the η 2 ‐thiocarbamoyl palladium complex [Pd(PPh 3 ) 2 (η 2 ‐SCNMe 2 )][PF 6 ], 1 with (EtO) 2 PS 2 NH 4 , Et 2 NCS 2 Na, and pySK in methanol at room temperature, respectively. Treatment of 1 with dppm (dppm: bis(diphenylphosphino)methane) in dichloromethane at room temperature gives complex [Pd(PPh 3 )(η 1 ‐SCNMe 2 )(η 2 ‐dppm)] [PF 6 ], 5 . All of the complexes are identified by spectroscopic methods and complex 1 is determined by single‐crystal X‐ray diffraction.