Structural Diversity and Rare η Cu-C Interactions in Cu Complexes of 1,2,3-Triazole-Functionalized Bisphosphines.

This manuscript describes the synthesis of copper complexes of 1,2,3-triazolyl-phosphines: -PhP(CH){1,2,3-NCCH)C(PPh)} (), (CH){1,2,3-NC(CH(-PPh))-C(PPh)} (), 3-PhP(CHN){1,2,3-NC(CH)C(PPh)} (), -PhP(CH){1,2,3-NC(CHN)C(PPh)} (), and {(3,5-PhPCH-)1,2,3-NCCH} (). The reactions of - with Cu salts afforded dimeric complexes having the general formula [Cu(μ -X)L] (L = , X = Cl, Br and I: - ; L= , X = Cl, Br and I: - ; L = ; X = Cl, Br, and I: -). The reaction of with CuI in a 1:2 molar ratio afforded 1D-coordination polymer [{(CuI){-PhP(CH){1,2,3-NC(CHN)C(PPh)}((-)(-))}}] ().

Catalytic utility of PNN-based Mn pincer complexes in the synthesis of quinolines and transfer hydrogenation of carbonyl derivatives.

This manuscript describes the synthesis of a triazolyl-pyridine-based phosphine, -((diphenylphosphaneyl)methyl)--methyl-6-(1-phenyl-1-1,2,3-triazol-4-yl)pyridin-2-amine, [2,6-{(PPh)CHN(Me)(CHN)(CHNCH)}] (1) (here onwards referred to as PNN) and its cationic and neutral Mn complexes and catalytic applications. The reaction of 1 with Mn(CO)Br afforded a cationic complex [Mn(CO)(PNN)]Br (2), which is highly stable in solid state, but in solution it gradually loses one of the CO groups to form a neutral complex [Mn(CO)(PNN)Br] (3). Complex 2 on treatment with AgBF also yielded a cationic complex [Mn(CO)(PNN)]BF (4).

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.

2,2'-Bipyridine derived doubly B ← N fused bisphosphine-chalcogenides, [CHN(BF){NCHP(E)Ph}] (E = O, S, Se): tuning of structural features and photophysical studies.

2,2'-Bipyridine based bisphosphine [CHN{N(H)CHPPh}] (1) and its bischalcogenide derivatives [CHN{N(H)CHP(E)Ph}] (2, E = O; 3, E = S; 4, E = Se) were synthesized, and further reacted with BF·EtO/EtN to form doubly B ← N fused compounds [CHN(BF){NCHP(E)Ph}] (5, E = O; 6, E = S; 7, E = Se) in excellent yields. The influence of the PE bonds on the electronic properties of the doubly B ← N fused systems and their structural features were investigated in detail, supported by extensive experimental and computational studies. Compound 6 exhibited a very high quantum yield of = 0.

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.

Synthesis, structural, characterization and Hirshfeld analysis of a bisselenide and a zinc complex of a new hemilabile ferrocenylbisphosphane, [Fe{CHP(CHCHNMe-o)}].

The novel hemilabile ferrocenylbisphosphane 1,1'-bis(bis{2-[(dimethylamino)methyl]phenyl}phosphanyl)ferrocene, [Fe{CHP(CHCHNMe-o)}] (1), was synthesized by reacting bis(dichlorophosphanyl)ferrocene, [Fe{CH(PCl)}] with LiCHCHNMe-o. Treatment of 1 with gray selenium and anhydrous ZnCl yielded, respectively, the bisselenide (ferrocene-1,1'-diyl)bis(bis{2-[(dimethylamino)methyl]phenyl}phosphine selenide), [Fe(CHNPSe)] (2), and the dizinc complex [μ-1,1'-bis(bis{2-[(dimethylamino)methyl]phenyl}phosphanyl)ferrocene-κN,P:κN',P']bis[dichloridozinc(II)] dichloromethane monosolvate, [FeZnCl(CHNP)]·CHCl (3), and both have been structurally characterized. Both compounds crystallized with the asymmetric unit containing half a molecule and with the Fe atom on an inversion centre.

Recent advances in organophosphorus-chalcogen and organophosphorus-pincer based macrocyclic compounds and their metal complexes.

The design and development of phosphorus based macrocycles containing one or more other heteroatoms is of crucial importance for the enhancement of modern synthetic chemistry. In recent years focus on phosphorus based macromolecules has led to intriguing and innovative structures with a variety of applications, including photophysical and host-guest properties, and in organic synthesis. This article summarizes the recent advancements in the synthesis of macrocycles that consist of organophosphorus-chalcogen (P-E, P[double bond, length as m-dash]E; E = O, S, Se) and organophosphorus-pincer based macrocyclic ligands and their transition metal complexes with emphasis given to synthetic methodologies.

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)] ().

Diverse Architectures and Luminescence Properties of Group 11 Complexes Containing Pyrimidine-Based Phosphine, -((Diphenylphosphine)methyl)pyrimidin-2-amine.

In this article, the synthesis, structural studies, and luminescence properties of Cu, Ag, and Au complexes of pyrimidine-based phosphine [CHN-2-NH(CHPPh)] () are described. The reactions of with CuX led to the isolation of one-dimensional (1D) chain, tetranuclear ladder, or cyclic derivatives. The structural features of these complexes are greatly influenced by the metal-to-ligand ratio, reaction conditions, and CuX (X = Cl, Br or I) employed.

Synthesis of tetra-pincer nickel(ii) and palladium(ii) complexes of resorcin[4]arene-octophosphinite [Res(OPR)] and rhodium-catalyzed regioselective hydroformylation reaction.

The condensation reaction of resorcinol with pentanal yielded resorcin[4]arene 1 which on bromination using N-bromosuccinimide at room temperature produced tetra-bromide derivative 2. The reactions of 2 with chlorodiphenylphosphine and o-phenylenephosphoro-chloridite yielded octaphosphinite 3 (hereafter referred to as octaphos) and octaphosphite 4, respectively. The reactions of 3 with Ni(COD)2 or Pd2(dba)3·CHCl3 in appropriate molar ratios yielded tetra-pincer complexes 5 and 6, respectively.