Ni, Pd and Pt pincer complexes of 2-(diphenylphosphanyl)--(2-(diphenyl-phosphanyl)benzyl)benzamide: synthesis, reactivity and catalytic studies.

In this article, the synthesis of bis(phosphine), -PhPCHC(O)N(H)CHCHPPh- (1) (hereafter referred to as "PNHP" and its anionic form as "PNP") and its group 10 metal chemistry and catalytic studies are described. PNHP (1) on reaction with NiCl(DME) and PdCl(COD) afforded pincer complexes, [MCl{(PNP)κ-,,}] (M = Ni, 2; Pd, 3). A similar reaction of 1 with PtCl(COD) yielded a chelate complex, [PtCl{(PNHP)κ-,}] (4), which on further treatment with LiHMDS produced the 1,2-azaphospholene-phosphine complex, [PtCl(Ph){(-P(Ph)CHCONCHCHPPh-)κ-,}] (5) P-C/P-N bond metathesis.

Arene displacement, C-H activation and acetonitrile insertion reactions enabled by coordination of a functionalized iminophosphorane to a Ru--cymene scaffold.

Reaction of a sterically demanding iminophosphorano-phosphine, PhPCHPhPNAr* (here onwards referred to as PCPNAr*; Ar* = 2,6-dibenzhydryl-4-methylphenyl), (1) with [Ru(η--cymene)Cl] yielded three different types of complex, [RuCl{(η--cymene)(PCPNAr*)-κ-}] (2), [RuCl{(P(O)CPNAr*)(κ-,)(-η-arene)}] (3) and [RuCl{(POCPNAr*)(κ-,)(-η-arene)}] (4), depending on the reaction conditions CH activation, tethered η-arene coordination, -metallation or PN bond cleavage/rearrangement reactions. Interestingly, a similar reaction in CHCN in the presence of AgBF resulted in the insertion of CHCN into the PN bond to form a novel metallacycle [Ru(NCMe){(PCPN(CH)CNAr*)-κ-,,}][BF] (5) containing 4- and 5-membered rings an aza-Wittig type reaction. Complex 4 showed very good catalytic activity in the transfer hydrogenation of carbonyl compounds.

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes.

Recent success in the synthesis of π-conjugated heavier pnictogen (As, Sb, and Bi) compounds and their transition metal complexes has led to the current surge in interest that led to significant development in the field of photophysical and optoelectronic properties of heavier pnictogens and their transition metal complexes. The presence of heavier pnictogens (As, Sb and Bi) in the molecular skeleton promotes inter-system crossing (ISC) and reverse inter-system crossing (RISC), because of the heavy atom effect, via altering the intermolecular interactions and orbital energy levels. As a result, π-conjugated heavier pnictogen compounds such as arsines, dibenzoarsepins, arsinoquinoline, heterofluorene, benzo[b]heterole (heterole=arsole, bismole, and stibole) show unique optoelectronic properties such as narrow bandgap, low-energy absorption, and long-wavelength emission than lighter pnictogen-based compounds.

Novel 1,2,3-triazolyl phosphine with a pyridyl functionality: synthesis, coinage metal complexes, photophysical studies and Cu(I) catalyzed C-O coupling of phenols with aryl bromides.

This manuscript describes the synthesis and coinage metal complexes of pyridine appended 1,2,3-triazolyl-phosphine [2-{(CHN)(C(PPh)NCH)}] (1), photophysical studies and their catalytic application. The reactions of 1 with copper salts afforded dimeric complexes [{Cu(μ-X)}{2-(CHN)(C(PPh)NCH)}] (2, X = Cl; 3, X = Br; and 4, X = I). The crystal structure indicates that the Cu⋯Cu distance in 4 (2.

Ru complexes of 1,2,3-triazole appended tertiary phosphines, [P(Ph){(-CH)(1,2,3-NC(Ph)CH}] and [P(Ph){-CH(CCH)-(1,2,3-N-Ph)}]: highly active catalysts for transfer hydrogenation of carbonyl/nitro compounds and for α-alkylation of ketones.

The synthesis of two new 1,2,3-triazole appended monophosphines [P(Ph){(-CH)(1,2,3-NC(Ph)CH}] (1) and [P(Ph){-CH(CCH)(1,2,3-N-Ph)}] (2) and their Ru complexes is described. The reactions of 1 and 2 with [Ru(PPh)Cl] in a 1 : 1 molar ratio produced cationic complexes 3 and 4, respectively. Both the complexes showed very high catalytic activity towards transfer hydrogenation, nitro reduction, and α-alkylation reactions and afforded the corresponding products in good to excellent yields.

1,2,3-Triazole based ligands with phosphine and pyridine functionalities: synthesis, Pd and Pt chemistry and catalytic studies.

This manuscript describes the syntheses of pyridine appended triazole-based mono- and bisphosphines, [-PhP(CH){1,2,3-NC(Py)C(H)}] (2), [-Br(CH){1,2,3-NC(Py)C(PPh)}] (3), [CH{1,2,3-NC(Py)C(PPh)}] (4), [PhP(CH){1,2,3-NC(Py)C(PPh)}] (5) and [3-PhP-2-{1,2,3-NC(Ph)C(PPh)}CHN] (6), their palladium and platinum chemistry and catalytic applications. These ligands upon treatment with [M(COD)Cl] (M = Pd or Pt) yielded complexes with different coordination modes, depending on the reaction conditions. Both κ-, and κ-, coordination modes were observed in many of the complexes indicating the ambidentate nature of these ligands.

Group 11 metal complexes of the dinucleating triazole appended bisphosphine 1,4-bis(5-(diisopropylphosphaneyl)-1-phenyl-1-1,2,3-triazol-4-yl)benzene.

The synthesis of a triazole appended dinucleating bisphosphine 1,4-bis(5-(diisopropylphosphaneyl)-1-phenyl-1-1,2,3-triazol-4-yl)benzene (2) and its coinage metal complexes are described. The dinucleating bisphosphine 2 was obtained by the temperature-controlled lithiation of 1,4-bis(1-phenyl-1-1,2,3-triazol-4-yl)benzene (1a) and 1,4-bis(1-(2-bromophenyl)-1-1,2,3-triazol-4-yl)benzene (1b) followed by the reaction with PrPCl. The reactions of 2 with copper(I) halides in 1 : 2 molar ratios yielded the [Cu(μ-X)] dimeric complexes [{Cu(μ-X)}(PPrNPhC)CH] (3, X = Cl; 4, X = Br; and 5, X = I), whereas the reaction of 2 with AgBr resulted in the formation of hetero-cubane complex [{Ag(μ-Br)}{(PPrNPhC)CH}] (7).

Rare Au···H Interactions in Gold(I) Complexes of Bulky Phosphines Derived from 2,6Dibenzhydryl-4-methylphenyl Core.

Gold(I) complexes of sterically demanding phosphines derived from 2,6-dibenzhydryl-4-methylphenyl core : 2,6-dibenzhydryl-,-bis((diphenylphosphane)-methyl)-4-methylaniline (), (2,6-dibenzhydryl-4-methylphenyl)-diphenylphosphane (), -(2,6-dibenzhydryl-4-methylphenyl)-1,1-diphenylphosphanamine (), and (2,6-dibenzhydryl-4-methylphenoxy)-diphenylphosphane () are described. The reaction of with 2 equiv of [AuCl(SMe)] in dichloromethane yielded [{AuCl}{Ar*N(CHPPh)}] (), which on further treatment with 2 equiv of AgSbF and 1 equiv of produced 12-membered dimeric complex [Au{μ-(Ar*N(CHPPh))}][(SbF)] (). A similar reaction of with AgSbF in CHCN afforded [{Au(NCCH)}{Ar*N(CHPPh)}][(SbF)] ().