Rhodium and Iridium Complexes Derived fromtrans-[MCl(CO)(PPh3)2] (M = Rh, Ir) and Pyridine-2-thiolate or 4,6-Dimethylpyrimidine-2-thiolate Ligands:S-Monodentate Coordination versusS,N-Chelation andS,N-Bridging; Reactivity oftrans-[Ir(‘Spy’)(CO)(PPh3)2] andtrans-[Ir(‘SpymMe2’)(CO)(PPh3)2] towards Acid

Effects of the Heterocycle and Its Substituents on Structure and Fluxionality in Rhodium(I) and Iridium(I) Complexes with the Hindered Thiolates 6-tert-Butylpyridine-2-thiolate and 1-Alkyl-4-tert-butylimidazole-2-thiolate (alkyl = methyl andtert-butyl)

“…Thus, the IR spectra of both compounds in dichloromethane showed three ν(CO) bands for the terminal carbonyl groups at 2082 (m), 2064 (s), and 2016 (s) cm -1 (compound 3 ) and 2073 (m), 2053 (s), and 2002 (s) cm -1 (compound 4 ). This pattern of intensities (m, s, s) is typical for tetracarbonyl dinuclear complexes having thiolato ligands as bridges and is distinct from that seen for cis -HT dimers of type E …”

“…Coordination of pyridine-2-thiolate (PyS) to Rh(I) and Ir(I) species as in M 2 (PyS) 2 L 1 L 2 , where L 1 and L 2 are CO, alkenes, or CO and phosphine, has established that doubly bridged species of types C and E could be formed and may interconvert in solution . The closely related species 1-alkylimidazole-2-thiolate has to our knowledge not been examined on Rh(I) or Ir(I), although it has shown a variety of coordination modes in other systems. − In the work reported here, we chose to increase steric hindrance at the basic heterocyclic nitrogen by using derivatives with an adjacent tert -butyl group.…”

Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

“…The yields of these two-dimensional sheet materials reached 50 and 90% for the chloride and bromide derivatives respectively. If these same reagents are allowed to react together for more than a month at room temperature, or they are heated under reflux in methanol for one day, further reaction occurs and the corresponding betain-containing materials, [Cu(ppt)Cl] n (7) or [Cu(ppt)Br] n (8) are formed (see Schemes 1 and 2). During this process the dpds ligands are converted into the coordinated betain, 1-(2-pyridyl)pyridinium-2-thiolate (ppt), with accompanying extrusion of elemental sulfur.…”

“…1 Pyridine-2-thiol (Hpyt) and pyridine-2-thiolate (pyt) are particularly versatile sulfur-containing ligands 2 and a number of studies have appeared that illustrate this point. [3][4][5][6][7][8][9] For example, copper() reacts with pyt to form the hexanuclear complex, [Cu(µ-pyt)] 6 10,11 and Hpyt can act as a bidentate ligand bridging between two metals to make either homo-or hetero-nuclear bimetallic complexes. 12- 17 Umakoshi et al have investigated the catalytic cleavage of sulfur from Hpyt using [Pt(5-mpyt) 2 Pt] (5mpyt = 5-methylpyridine-2-thiolate).…”

Preparation of mononuclear and dinuclear Rh hydrotris(pyrazolyl)borato complexes containing arenethiolato ligands and conversion of the mononuclear complexes into dinuclear Rh–Rh and Rh–Ir complexes with bridging arenethiolato ligands

“…), 9 [{RhCl(l-SPy-S,N )(g 1 -NHC 5 H 4 S)(CO)} 2 ], 10 [{Rh(CO)(PPh 3 )} 2 (l-SPy-S,N ) 2 ], 11 and [{Cp*Rh(l-SPym-S,N )} 2 ] 12 as well as a mononuclear Rh compound [Rh(g 2 -SPym-4,6-Me 2 )(CO)(PPh 3 )]. 11 The S-S bond scission was also observed in the reaction of 1 with tetraethylthiuram disulfide Et 2 NC(S)SSC(S)NEt 2 undersimilar conditions, affording the mononuclear bis(dithiocarbamato) complex [Tp*Rh(g 2 -S 2 CNEt 2 )(g 1 -S 2 CNEt 2 )] ( 7), which has been characterized by spectroscopic and analytical data along with X-ray analysis (Scheme 1). The 1 H NMR spectrum of 7 at room temperature shows clearly the presence of the two types of S 2 CNEt 2 ligands.…”