Metal-metal bonded compounds. V. Compounds with Ir (Rh)-Hg bonds containing a bridging and a chelating triazenido group which interconvert intramolecularly

The compounds [(Diene)(RN{3}R'){2}MHgCl]{2} (M = Ir; Diene = COD; R = CH{3}, C{2}H{5}; R' = p-CH{3}C{6}H{4} and M = Rh; Diene = COD, NOR; R = CH{3}, C{2}H{5}, p-CH{3}-C{6}H{4}; R' = p-CH{3}C{6}H{4} have been prepared by reaction of [(Diene)MCl]{2} with [Hg(RN{3}R'){2}] and by reaction of [{(Diene)MCl}(HgCl{2})]{2} with [Ag(RN{3}R')]{n}. A crystal structures study of [(COD)(EpTT){2}IrHgCl]{2} shows that the complex is dimeric with two chloride atoms bridging the two mercury atoms. In each half of the dimer there is one triazenido group chelating to the Ir atom and one triazenido group bridging an iridium-mercury bond (2.62 @9). The complexes are monomeric in solution but have otherwise a configuration around the Ir(Rh)atom similar to that in the solid state. Fluxional processes, which occur for M = Rh but not for M = Ir, involve a novel dynamic process consisting of interchange of the bridging and chelating triazenido groups via monodentate intermediates

s,s'-N,N' bridging and s,s-N,N chelating a-diimines. Molecular geometries of[PtCl2PBu3]2 (t-BuN=CHCH=NBu-t) and PtCl2 (styrene)(t-BuN=CHCH=NBu-t)

X-ray structure analysis of [PtCl{2}PBu{3}]{2}(t-BuN@?CHCH@?NBu-t) has shown the presence of @s, @s'-N,N'-bonded diimine, which bridges in the anticonfiguration two planar trans-PtCl{2}PBu{3}N moieties. The crystal structure of PtCl{2}(styrene)(t-BuN@?CHCH@?NBu-t) contains a unidentate-bonded styrene molecule in the equatorial position of a trigonal bipyramidal arrangement with the phenyl ring bent back by 27}o{

Synthesis andmolecular geometry of [trans-PtCl2PBu3]2 (di-t-Bu-diimine) containing a s,s-N,N' bridging diimine with a planar anti-(trans-P-Pt-NCCN-Pt-P-trans)-skeleton

Complexes of the type [MCl{2}XR'{3}]{2}R-dim (M = Pd or Pt; XR'{3} = arsine or phosphine) are formed in almost quantitative yield in the reactions of [MCl{2}XR'{3}]{2} with @a-diimine (11 molar ratio Pt-dimer/R-dim). An X-ray study of [PtCl{2}PBu{3}]{2}t-Bu-dim [Z = 2, a = 11.4540(11), b = 16.1169(7), c = 12.9202(12) @9 and @b = 99.82(1); R = 5.9%] reveals a structure consisting of two planar trans-PtCl{2}P-units bridged by a planar NCCN skeleton in anti-configuration [C@?C 1.48(2), C@?N 1.27(3), N@?Pt 2.214(10) @9]. As a consequence of the orthogonal position of the platinum coordination plane and the NCCN plane the @b-imine proton resides a short distance from the platinum atom (about 2.6 @9). The structure in solution has been determined by }1{H, }1{}3{C, }3{}1{P and }1{}9{}5{Pt NMR spectroscopy. The observed spectra point to retention of the structural features in solution as evidenced by a large down field shift of the imine protons, e.g. 9.58 ppm and an AA'MM' pattern in [PdCl{2}PEt{3}]{2}t-Bu-dim. The present compounds are the first examples of complexes which contain a @s, @s'-N,N' planar bridging diimine ligand as a general structural feature

Thermal and photochemical reactivity of manganese tricarbonyl and tetracarbonyl complexes with a bulky diazabutadiene ligand

10.1021/ic500025kInorganic Chemistry5384081-4088INOC