Late transition metal .mu.-oxo and .mu.-imido complexes. 5. Addition of methylene chloride and methyl iodide to the phenyl ring of aryl imido/amido complexes of rhodium

Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

“…Both 1 and 2 exhibit well‐resolved diamagnetic 1 H NMR spectra (Figure 1, and Figure S1 in the Supporting Information), featuring substantially upfield‐shifted H d and H d’ signals ( δ ≈4.3, 3.5 ppm) compared with the corresponding signals of arylamido complex [Ru IV (ttp)(NH‐ p ‐ClC 6 H 4 ) 2 ] ( δ =5.84 ppm10a), which is consistent with the attachment of H d and H d’ to a quinone‐like ring 5a,b. The large splitting of the H d and H d’ signals should stem from the prohibited rotation of the 2,6‐dimethylphenyl group about the directly attached CN bond (which also splits the Me 2 and Me 2’ signals as observed).…”

“…While there are a large number of metal complexes of quinoneimines known in the literature,3, 4 quinoneimido complexes of transition metals are sparse 5–7. In the early 1990s, Sharp and co‐workers5a,b reported di‐ or tetranuclear rhodium complexes analogous to bridging quinoneimido complexes. Subsequently, bridging quinoneimido ligands were reported to exist in a few di‐ or trinuclear osmium5c and palladium/platinum5d complexes and hexanuclear osmium complexes,5e with the oxidation states of the metal ions being +2 or less.…”

Osmium imido complexes: synthesis, reactivity, and SCF-X.alpha.-SW electronic structure

“…Anal. Calcd for C30H52N2O6OsP2: C, 45.68; H, 6.64; N, 3.55.Found: C, 45.69;H, 6.62; N, 3.54. 0s[(Ar)CH2CH2NAr](NAr)(0) (5a).…”

Nucleophilicity of Ligated S22-Ions. Conversion of Organic Chlorides into Organosulfur Compounds incis-[(MCp*)2(μ-CH2)2(μ-S2R)]+(M = Rh, Ir)

“…Chlorinated organic compounds, such as chloroform, dichloromethane, carbon tetrachloride, and 1,1,1-trichloroethane, used in chemical laboratories, industries, electrical appliances, etc., are toxic, and some of them pose health hazards . The activation of carbon−chlorine bonds using chemical, microbial, or thermal methods, for converting organic halides into either less toxic or industrially useful materials, is an interesting area of research activity. − Very electron rich centers are required to produce rupture of the strong C−Cl bonds, such as those of CH 2 Cl 2 or CHCl 3 , , and the oxidative addition of chlorocarbons to metal complexes is the initial step for their activation either by further transfer to organic molecules or by their functionalization in possible catayltic processes . Among various metals, rhodium and iridium complexes have shown good reactivity toward chloroalkanes, for oxidative-addition reactions at their metal centers. − ,− …”

“…Thiolate anions S n 2- ( n = 1, 2, 3) can convert alkyl chloride into dialkyl oligosulfane by activation of the C−Cl bonds . Several metallosulfur systems are reported to react with chlorinated hydrocarbons; however, there is no report on mono- or multi-C−Cl bond activation by the insertion to the S−S bond of the coordinated S 2 ligand. − The S 2 ligand coordinated to the metal dinuclear unit in parallel in dinuclear cis- [(MCp*) 2 (μ-CH 2 ) 2 (μ-S 2 )] (Scheme : 1 , Rh; 2 , Ir, Cp* = C 5 Me 5 ) has high nucleophilicity, as noted toward dioxygen, and could be useful in activating C−Cl bonds. − Thus, using compound 2 , we have explored the novel multibond activation of C−Cl (or C−Cl and C−H) bonds in (1,1,1-trichloromethyl)benzene (C 6 H 5 CCl 3 ), (1,1-dichloromethyl)benzene (C 6 H 5 CHCl 2 ), and mono-chloromethylbenzene (C 6 H 5 CH 2 Cl) . In this paper, we report reactions of compound 1 with C 6 H 5 CCl 3 and p -ClC 6 H 4 CCl 3 as well as those of compound 2 with p -Cl-C 6 H 4 CCl 3 and carbon tetrachloride.…”