Synthesis, characterization, and reactivity of phosphine- and arsine-bridged dirhodium complexes containing bridging pyrazolate and triazolate ligands

Abstract

4597The chemical reactivity of the compounds is much greater than the corresponding chlorine analogues. Both N-bromo derivatives react with AgCl, forming the respective silver salts and BrCl, and with chloroform, liberating BrCl. As expected, their reactivity does not approach that of BrOSOzF with covalent chlorides: BrOSOZF reacts rapidly with CFCl, at 22 OC, whereas solutions of the new N-bromo compounds appear to be stable a t 22 O C .Characterization of the new compounds is given in the experimental section, with the IR, N M R , Raman, and mass spectra being similar t o those of t h e respective a n a l o g u e s (CF3S0z)zNCI'1~1Z and (FS02)zNC1.'3.'7*18 Assignment of frequencies to vN-x in this series is not obvious.

Linear Metal−Metal-Bonded Tetranuclear M−Mo−Mo−M Complexes (M = Ir and Rh): Oxidative Metal−Metal Bond Formation in a Tetrametallic System and 1,4-Addition Reaction of Alkyl Halides

“…18 We are interested in the versatility of metal-metal bond formations as well as their reaction mechanism in our heteronuclear tetranuclear system. Although metal-metal bond formations have been given by one-electron oxidation of each terminal metal in dinuclear complexes having no metal-metal bond, [19][20][21][22][23][24][25][26][27] comparable studies on multinuclear complexes composed of more than three transition metals are relatively rare. 5d,f Preliminary results obtained for the first synthesis of novel tetranuclear Rh-Mo-Mo-Rh arrays and oxidation of Rh(I) atoms to Rh(II) atoms, which induced formation of Rh-Mo bonds, were reported earlier, 28 and an extended and full account of the synthesis and reactivity of linearly aligned tetranuclear complexes bearing the M(I)‚‚‚ Mo(II)-Mo(II)‚‚‚M(I) skeleton (M ) Ir and Rh) is presented here.…”

m-nitrobenzyl alcohol electrochemistry in fast atom bombardment mass spectrometry

“…The dirhodium complexes were synthesized, isolated, and purified by methods described elsewhere [43,44]. All other chemicals were reagent grade and were used as received, except as noted.…”

“…Thus, although knowledge of this matrix chemistry could clarify our understanding of the FAB ionization process, monitoring it with normal electrochemical probes is very difficult, if not impossible. This study seeks to investigate the intrinsic and bombardment-induced redox behavior of NBA in FAB/MS by a bracketing approach [9] for a series of pyrazolate-bridged dirhodium A-frame complexes, M(PF 6 )w where n = 1 or 2, and M is the cation represented by Structure I [43,44]-The complexes contain an apex pyrazolate anion (2), and various transoid bridging (EE') and terminal (L) ligands (Table 1 and Structure I). One of the central Rh atoms may be in either the 1 + or 2 + nominal oxidation state, Rh(I) and Rh(II), respectively, while the other is always nominally Rh(I).…”

Selective N Functionalization of Methane and Ethane to Aminated Derivatives by Main-Group-Directed C–H Activation

“…To study the reaction N-functionalization mechanism without complications from oxy anions that generate Ofunctionalized products, the reaction of Hg II (NTf 2 ) 2 (which is isoelectronic with Tl III (NTf 2 ) 3 ) with methane was examined in HNTf 2 . Hg(NTf 2 ) 2 is a known compound that can be synthesized, 20 free of all oxy anions. Reactions of Hg II (NTf 2 ) 2 in Tf 2 NH were carried out at 180 °C with 1000 psig of CH 4 (Figure 2A and Table S1, entry 4).…”

“…This reaction showed no detectable (±5% D-incorporation detection limit) deuterium incorporation into the gas-phase CH 4 . The reaction was also found to proceed in HN­(SO 2 F) 2 with the corresponding, previously characterized Hg­(NSO 2 F) 2 salt . Using this less sterically hindered nitrogen acid with a comparable acidity to HNTf 2 , the reaction yield with methane was found to increase to 48% with the observation of MeN­(SO 2 F) 2 (45%) and MeHg­(N­(SO 2 F) 2 ) (3%) (Figure C and Table S1, entry 7).…”