Structural Diversity and Rare η1 Cu-C Interactions in CuI Complexes of 1,2,3-Triazole-Functionalized Bisphosphines.

This manuscript describes the synthesis of copper complexes of 1,2,3-triazolyl-phosphines: o-Ph2P(C6H4){1,2,3-N3CC6H5)C(PPh2)} (L1), (C6H5){1,2,3-N3C(C6H4(o-PPh2))-C(PPh2)} (L2), 3-Ph2P(C5H3N){1,2,3-N3C(C6H5)C(PPh2)} (L3), o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)} (L4), and {(3,5-Ph2PC6H4-o)21,2,3-N3CCH} (L5). The reactions of L1-L3 with CuI salts afforded dimeric complexes having the general formula [Cu2(µ -X)2L2] (L = L1, X = Cl, Br and I: 1 - 3; L= L2, X = Cl, Br and I: 4- 6; L = L3; X = Cl, Br, and I: 7-9). The reaction of L4 with CuI in a 1:2 molar ratio afforded 1D-coordination polymer [{(CuI)2{o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)}-µ-((k1-N)(k2-P,P))}}]n (10). The reaction of L5 with cuprous halides (CuX) (X = Br, I) yielded mononuclear complexes [CuX{(3,5-Ph2PC6H4-o)21,2,3-N3CCH}-κ2P,P] (X = Br, 12; I, 13). Crystal structures of complexes 12 and 13 showed close interactions between CuI and the triazole C7 carbon. These relatively short Cu···C7 separations may be due to the η1-C interaction (dπ-pπ bond) between the triazolic carbon atom (via pz orbital) and CuI or three-centered two-electron interaction between CuI and the triazolic C-H bond. The existence of the Cu···C interaction was further evinced by the QTAIM analysis in compounds 12 and 13.

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-{(C6H4N)(C2(PPh2)N3C6H5)}] (1), photophysical studies and their catalytic application. The reactions of 1 with copper salts afforded dimeric complexes [{Cu(µ2-X)}2{2-(C6H4N)(C2(PPh2)N3C6H5)}2] (2, X = Cl; 3, X = Br; and 4, X = I). The crystal structure indicates that the Cu⋯Cu distance in 4 (2.694 Å) is significantly shorter than that in complexes 3 (3.0387 Å) and 2 (3.104 Å), indicating strong cuprophilic interactions which is also supported by NBO calculations, signifying the involvement of 3dz2 orbitals from each Cu atom contributing to the bonding interaction. The fluorescence studies on complexes 2-4 carried out in the solid state showed broad emission bands around 560 nm on excitation at λex = 420 nm. Complex 4 on treatment with two equivalents of 1,10-phenanthroline yielded a mononuclear complex 5 which showed almost complete quenching of fluorescence in the solid state, clearly indicating that the emissive properties of 4 are mainly due to the Cu⋯Cu interaction, along with (M + X)LCT. The reactions of 1 with silver salts led to the isolation of dimeric complexes [{Ag(µ2-X)}2{2-(C6H4N)(C2(PPh2)N3C6H5)}2] (6, X = Cl; 7, X = Br; and 8, X = I) in good yield. The reaction between 1 and [AuCl(SMe2)] yielded [{AuCl}{2-(C6H4N)(C2(PPh2)N3C6H5)}] (9). The molecular structures of 2-5 and 7-9 were confirmed by single crystal X-ray analysis. The complex 4 is found to be an excellent catalyst for C-O coupling under mild conditions.

RuII complexes of 1,2,3-triazole appended tertiary phosphines, [P(Ph){(o-C6H4)(1,2,3-N3C(Ph)CH}2] and [P(Ph){o-C6H4(CCH)-(1,2,3-N3-Ph)}2]: 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){(o-C6H4)(1,2,3-N3C(Ph)CH}2] (1) and [P(Ph){o-C6H4(CCH)(1,2,3-N3-Ph)}2] (2) and their RuII complexes is described. The reactions of 1 and 2 with [Ru(PPh3)3Cl2] 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. The free energy of ß-hydride elimination from the respective Ru-alkoxide intermediates, a key mechanistic step common to all the three catalytic pathways, was calculated to be close to ergoneutral by density functional theory-based calculations, which is posited to rationalize the catalytic activity of 3. The reduction of aromatic nitro compounds was found to be highly chemoselective and produced the corresponding amines as major products even in the presence of a carbonyl group. The triazolyl-N2 coordinated RuII-NPN complex 3 showed better catalytic activity compared to the triazolyl-N3 coordinated complex 4.

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

This manuscript describes the syntheses of pyridine appended triazole-based mono- and bisphosphines, [o-Ph2P(C6H4){1,2,3-N3C(Py)C(H)}] (2), [o-Br(C6H4){1,2,3-N3C(Py)C(PPh2)}] (3), [C6H5{1,2,3-N3C(Py)C(PPh2)}] (4), [Ph2P(C6H4){1,2,3-N3C(Py)C(PPh2)}] (5) and [3-Ph2P-2-{1,2,3-N3C(Ph)C(PPh2)}C5H3N] (6), their palladium and platinum chemistry and catalytic applications. These ligands upon treatment with [M(COD)Cl2] (M = Pd or Pt) yielded complexes with different coordination modes, depending on the reaction conditions. Both κ2-P,N and κ2-P,P coordination modes were observed in many of the complexes indicating the ambidentate nature of these ligands. Monophosphine 2 in the presence of a base afforded rare fused-5,6-membered PCN pincer complexes [MCl{o-Ph2P(C6H4){1,2,3-N3C(Py)C(H)}}-κ3-P,C,N] (7, M = Pd; 8, M = Pt), whereas the reactions of 4 with [M(COD)Cl2] (M = Pd, Pt) produced κ2-P,N chelate complexes [MCl2{C6H5{1,2,3-N3C(Py)C(PPh2)}-κ2-P,N}] (9, M = Pd; 10, M = Pt). Similar reactions of 5 and 6 resulted in κ2-P,P chelate complexes [MCl2{{3-Ph2P-2-{1,2,3-N3C(Ph)C(PPh2)}C5H3N}-κ2-P,P}] (11, M = Pd; 12, M = Pt) and [MCl2{3-Ph2P-2-{1,2,3-N3C(Ph)C(PPh2)}C5H3N}-κ2-P,P}] (13, M = Pd; 14, M = Pt), respectively. The palladium(II) complexes have shown excellent catalytic activity in the α-alkylation reaction of acetophenone derivatives.

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

The synthesis of a triazole appended dinucleating bisphosphine 1,4-bis(5-(diisopropylphosphaneyl)-1-phenyl-1H-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-1H-1,2,3-triazol-4-yl)benzene (1a) and 1,4-bis(1-(2-bromophenyl)-1H-1,2,3-triazol-4-yl)benzene (1b) followed by the reaction with iPr2PCl. The reactions of 2 with copper(I) halides in 1 : 2 molar ratios yielded the [Cu(µ2-X)]2 dimeric complexes [{Cu(µ2-X)}2(PiPr2N3PhC2)2C6H4] (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 [{Ag4(µ3-Br)4}{(PiPr2N3PhC2)2C6H4}2] (7). Similar reactions of 2 with AgX in 1 : 2 molar ratios yielded disilver complexes [{Ag(µ2-X)}2{(PiPr2N3PhC2)2C6H4}] (6, X = Cl and 8, X = I). Treatment of 2 with AgOAc in a 1 : 2 molar ratio afforded a dinuclear complex [Ag2(µ2-OAc)2{(PiPr2N3PhC2)2(C6H4)}] (9) with one of the acetate ligands bridging the two metal centres in the side-on mode, whereas the other one adopting the end-on mode keeping the >CO group uncoordinated. The reaction of 2 with two equivalents of [AuCl(SMe2)] afforded the digold complex [(AuClPiPr2N3PhC2)2C6H4] (10). The molecular structures of 2-5 and 7-10 were confirmed by single crystal X-ray analysis. Non-covalent interactions between Cu and Carene were observed in the molecular structures of 3, 4 and 5. These weak interactions were also assessed by DFT calculations in terms of their non-covalent interaction plots (NCI) and QTAIM analyses.

Novel approach to benzo-fused 1,2-azaphospholene involving a Pd(II)-assisted tandem P-C bond cleavage and P-N bond formation reaction.

New bisphosphine o-Ph2PC6H4C(O)N(H)C6H4PPh2-o (1) (Bala-HariPhos) showed a unique reactivity towards Pd(ii) resulting in a 1,2-azaphospholene complex, involving a tandem P-C bond cleavage, P-N bond formation and cyclization process via the elimination of PhH. Mechanistic details were investigated using NMR spectroscopy, DFT calculations and kinetic data, and by SCXRD analysis. It involves the reductive elimination from a tautomerised complex to form a phosphonium salt followed by oxidative addition.

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

Gold(I) complexes of sterically demanding phosphines derived from 2,6-dibenzhydryl-4-methylphenyl core viz: 2,6-dibenzhydryl-N,N-bis((diphenylphosphane)-methyl)-4-methylaniline (1), (2,6-dibenzhydryl-4-methylphenyl)-diphenylphosphane (2), N-(2,6-dibenzhydryl-4-methylphenyl)-1,1-diphenylphosphanamine (3), and (2,6-dibenzhydryl-4-methylphenoxy)-diphenylphosphane (4) are described. The reaction of 1 with 2 equiv of [AuCl(SMe2)] in dichloromethane yielded [{AuCl}2{Ar*N(CH2PPh2)2}] (5), which on further treatment with 2 equiv of AgSbF6 and 1 equiv of 1 produced 12-membered dimeric complex [Au2{µ-(Ar*N(CH2PPh2)2)2}][(SbF6)2] (6). A similar reaction of 5 with AgSbF6 in CH3CN afforded [{Au(NCCH3)}2{Ar*N(CH2PPh2)2}][(SbF6)2] (7). Equimolar reactions of bulky phosphines 2, 3, and 4 with [AuCl(SMe2)] resulted in [AuCl(PPh2Ar*)] (8), [AuCl(PPh2NHAr*)] (9), and [AuCl(PPh2OAr*)] (10). Complexes 9 and 10 on treatment with AgSbF6 in CH3CN produced the cationic complexes [Au(NCCH3)(PPh2NHAr*)][(SbF6)] (11) and [Au(NCCH3)(PPh2OAr*)][(SbF6)] (12), respectively. The molecular structure of complex 6 revealed the presence of a strong intramolecular aurophilic interaction with a Au···Au distance of 2.9720(4) Å. Careful analysis of molecular structure of 5 revealed the presence of rare Au···H-C (sp3) interactions between the gold(I) atom and one of the methylene protons of -NCH2PPh2 groups. The solution 1H NMR signals of the methylene protons of 5 showed a considerable downfield shift (∼1 ppm) compared to that of the free ligand indicating their interactions (Au···H) with the Au atom. Complexes 8 and 10 also showed Au···H interactions in their molecular structures. The existence of the Au···H interaction was studied by variable temperature 1H NMR data in the case of complex 5 and further evinced by the QTAIM analysis in complexes 5, 8, and 10.

New 1,2,3-triazole based bis- and trisphosphine ligands: synthesis, transition metal chemistry and catalytic studies.

The syntheses and transition metal chemistry of triazole-based bis- and tris-phosphines, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)phenyl)-4-phenyl-1H-1,2,3-triazole (2), 5-(diphenylphosphanyl)-4-(2-(diphenylphosphanyl)phenyl)-1-phenyl-1H-1,2,3-triazole (5), 1,4-bis(2-(diphenylphosphanyl)phenyl)-1H-1,2,3-triazole (6) and 5-(diphenylphosphanyl)-1,4-bis(2-(diphenylphosphanyl)phenyl)-1H-1,2,3-triazole (7), are described. Bisphosphines 5 and 6 show versatile coordination behavior due to the presence of at least four donor atoms. The reactions of 5 and 6 with group VI metal carbonyl derivatives were found to be highly sensitive to the reaction conditions. Bisphosphine 5 upon treatment with [M(CO)4(piperidine)2] (M = Mo and W) yielded both P,P and P,N coordinated complexes [M(CO)4(5)] [M = Mo-κ2-P,N (8); W-κ2-P,N (9); Mo-κ2-P,P (10); W-κ2-P,P (11)], whereas 6 afforded only P,N coordinated complexes [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))CH}-κ2-P,N}Mo(CO)4] (12) and [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))CH}-κ2-P,N}W(CO)4] (13). The reactions of 5 with [M(COD)Cl2] (M = Pd and Pt) yielded κ2-P,P chelate complexes 14 and 15, respectively, whereas the treatment of 6 with [Pd(COD)Cl2] at ambient temperature resulted in the formation of a rare fused six-membered PCP pincer complex [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))C}-κ3-P,C,P}PdCl] (16). Similar reactions of 6 with [NiCl2(DME)] and [Pt(COD)Cl2] in the presence of LiHMDS yielded [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))C}-κ3-P,C,P}NiCl] (17) and [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))C}-κ3-P,C,P}PtCl] (18), respectively. The reaction between 6 and [M(COD)Cl]2 (M = Rh and Ir) produced cationic complexes [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))CH}-κ2-P,N}Rh(C8H12)]Cl (19) and [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))CH}-κ2-P,N}Ir(C8H12)]Cl (20), respectively, whereas the reaction with [Rh(acac)(CO)2] resulted in a pincer complex [{o-Ph2P(C6H4){1,2,3-N3C(o-Ph2P(C6H4))C}-κ3-P,C,P}Rh(CO)] (21). The structures of most of the compounds have been determined by single crystal X-ray analyses. The fused six-membered PCP palladium pincer complex 16 is found to be an excellent catalyst for the Mizoroki-Heck coupling reaction.

Synthesis of Indoles and Benzofurans Using a Graphene Oxide-Grafted Aminobisphosphine-PdII Complex.

Indoles and benzofurans have been synthesized using a graphene oxide-grafted aminobisphosphine-PdII complex (GO@PNP-Pd) under copper-free condition. A range of indole and benzofuran derivatives have been made by the reaction of N-protected 2-iodoanilines and 2-iodophenols with terminal acetylenes in presence of GO@PNP-Pd. The activity of the aminobisphosphine-PdII complex remains the same under both homogeneous and heterogeneous conditions. Finally, the recycling ability of the immobilized catalyst (GO@PNP-Pd) has been examined for five consecutive runs with appreciable conversion.

1,2,3-Triazole based bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)-phenyl)-4-phenyl-1H-1,2,3-triazole: an ambidentate ligand with switchable coordination modes.

The reaction of 1-(2-bromophenyl)-4-phenyl-1H-1,2,3-triazole (1) with Ph2PCl yielded bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)phenyl)-4-phenyl-1H-1,2,3-triazole (2). Bisphosphine 2 exhibits ambidentate character in either the κ2-P,N or κ2-P,P coordination mode. Treatment of 2 with [M(CO)4(piperidine)2] (M = Mo and W) yielded κ2-P,N and κ2-P,P coordinated Mo0 and W0 complexes [M(CO)4(2)] [M = W-κ2-P,N (4); Mo-κ2-P,P (5); W-κ2-P,P (6)] depending on the reaction conditions. Formation and stability of κ2-P,P coordinated Mo0 and W0 complexes were assessed by time dependent 31P{1H} NMR experiments and DFT studies. The complex 4 on treatment with [AuCl(SMe2)] afforded the hetero-bimetallic complex [µ-PN,P-{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2AuCl)}-κ2-P,N}W(CO)4] (7). The 1 : 1 reaction between 2 and [CpRu(PPh3)2Cl] yielded [(η5-C5H5)RuCl{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2)}}-κ2-P,P] (8), whereas the similar reaction with [Ru(η6-p-cymene)Cl2]2 in a 2 : 1 molar ratio produced a cationic complex [(η6-p-cymene)RuCl{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2)}}-κ2-P,N]Cl (9). Similarly, treatment of 2 with [M(COD)(Cl)2] (M = Pd and Pt) in a 1 : 1 molar ratio yielded PdII and PtII complexes [{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2)}-κ2-P,P}PdCl2] (10) and [{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2)}-κ2-P,P}PtCl2] (11). The reaction of 2 with 2 equiv. of [AuCl(SMe2)] afforded [Au2Cl2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(PPh2)}}-µ-P,P] (12). Most of the complexes have been structurally characterized. Palladium complex 10 shows excellent catalytic activity towards Cu-free Sonogashira alkynylation/cyclization reactions.

First examples of tri- and tetraphosphametacyclophanes: synthesis and isolation of an unusual hexapalladium complex containing pincer units with Pd-P covalent bonds.

The synthesis of the first examples of tri- and tetraphosphametacyclophanes [m-{-C(O)C5H3N(C(O)PPh)}3 (1) and m-{-C(O)C5H3N(C(O)PPh)}4 (2)] is described. The reaction of 1 with [Pd(η3-C3H5)Cl]2 yielded a rare hexapalladium(ii) complex with four Pd-P covalent bonds.

Two Triazole-Based Phosphine Ligands Prepared via Temperature-Mediated Li/H Exchange: Cu(I) and Au(I) Complexes and Structural Studies.

The kinetically favored triazole-based phosphine 1-(2-(diphenylphosphino)phenyl)-4-phenyl-1H-1,2,3-triazole (2, L1) and its thermodynamically preferred isomer, 5-(diphenylphosphino)-1,4-diphenyl-1H-1,2,3-triazole (3, L2), were obtained by the temperature-controlled lithiation of 2-bromotriazole followed by the reaction with chlorodiphenylphosphine. The structures of phosphines 2 and 3 were determined by X-ray diffraction. Upon reaction with late transition-metal derivatives (Cu(I), Ag(I), and Au(I)), phosphines 2 and 3 form complexes with monodentate (Cu(I), Ag(I), and Au(I); κ(1)-P), chelate (Cu(I); κ(2)-P,N), bridged bidentate (Cu(I); µ(2)-P,N), and tridentate (Cu(I); µ(2),κ(2)-P,N,N) modes of coordination. Reactions with copper(I) halides produced mono-, di-, and tetranuclear complexes, whereas the reaction of 2 with [Cu(NCCH3)4]BF4 yielded the binuclear complex [Cu2(CH3CN)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-µ-(κ-P,κ-N),κ-N}2](BF4)2 (10) with the ligand acting as a six-electron donor involving phosphorus and two triazole nitrogen atoms. The copper complexes of 2 and 3 containing rhomboid Cu2X2 units, [(Cu)2(µ-X)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}2] (4, X = Cl; 5, X = Br), on treatment with 1,10-phenanthroline and 2,2'-bipyridine gave mixed-ligand complexes of the type [(CuX)(N∩N-κ(2)-N,N){o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}] (N∩N = 1,10-phen and 2,2'-bipy; X = Cl, Br, and I).