The interaction of organic isothiocyanates with complexes of ruthenium and rhodium. Formation of Π-bound isothiocyanate, isonitrile-dithiocarbonimidato complexes and a new route to isonitrile-dioxygen complexes of rhodium.

Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

“…6 , Scheme 2 ). The assembly of a dithiocarbonimidate ligand via this reaction is remarkable, as in the coordination sphere of a metal it was only achieved by a [2 + 2] addition of organo isothiocyanates with transient terminal metal sulfides 40 or oxidation of isonitriles with metal persulfides. 41 The formation of [2] − resembles the insertion of a carbodiimide into the iron( ii ) imide bond of the nucleophilic [(Ph 2 B( t BuIM) 2 )Fe(NDipp)] − .…”

Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates

“…On the other hand, several Pd(0) complexes such as [Pd 2 (dba) 3 ]$CHCl 3 [30] (in the presence of PPh 3 ) and [Pd(PR 3 ) n ] [31] (n ¼ 4 for PMe 3 , PMe 2 Ph, PMePh 2 ; n ¼ 2 for P(i-Pr) 3 ) were shown to react with ReNCS (R ¼ Me, Ph, C(O)OEt) to give only the dithiocarbonimidato Pd complexes [Pd(S 2 C]NeR)(PR 3 ) 2 ]. Several earlier works also showed that the low-oxidation-state Pt [32], Ru [33] and Rh [34] In order to gain insight into the formation of dithiocarbonimidato or diphenylsilyl complexes, we further examined the chemical reactivity of organic isothiocyanates toward other Pd compounds of tertiary phosphines. We have already reported that reactions of trans-[PdEt 2 L 2 ] with H 2 SiPh 2 gave the silyl-bridged dinuclear Pd complexes [Pd(mHSiPh 2 )L] 2 (L ¼ PMe 3 , etc.)…”

Transformations of aryl isothiocyanates on tetraphosphine tungsten complexes and reactivity of the resulting dithiocarbonimidate ligand

“…Such bond recombinations of RNCS have been known mostly for group 8-10 metal complexes in low oxidation states. Complexes of the type [M(S 2 CNR)(CNR)L n ] have been obtained selectively by the reactions of Ru(0) 19 Rh(I), 19,20 and Pt(0) 21 complexes. In the cases of Pd(0), Pt(0) and their precursors, the concomitantly formed isocyanide dissociated from the metal to result in dithiocarbonimidate complexes.…”