ABSTRACT Graphical abstract The photophysical properties of triphenylphosphole-chalcogenides is d... more ABSTRACT Graphical abstract The photophysical properties of triphenylphosphole-chalcogenides is described.
Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(micro-NtBu)}2 (1a-1... more Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(micro-NtBu)}2 (1a-1d) produce binuclear gold(I) complexes of the type, [ClAu{RP(micro-NtBu)}2AuCl] (2 R=OC6H4OMe-o, 3R=OCH2CH2OMe, 4R=NEt2, 5R=NHtBu) in quantitative yield. A similar reaction between cis-{(o-MeOC6H4O)P(micro-NtBu)}2 (1a) and [AuCl(SMe2)] in a 1:1 molar ratio afforded the mono-nuclear complex [ClAu{(o-MeOC6H4O)P(micro-NtBu)}2] (6). Addition of two equivalents of CuX (X=Br, I) to the chloro derivative 2 leads to the formation of bromo, [BrAu{(o-MeOC6H4O)P(micro-NtBu)}2AuBr] (7), and iodo, [IAu{(o-MeOC6H4O)P(micro-NtBu)}2AuI] (8), derivatives through halogen exchange reactions. A tetranuclear gold(I) macrocycle [Au{(o-MeOC6H4O)P(micro-NtBu)}2]4(ClO4)4 (9) and a mononuclear gold(I) complex [Au({(o-MeOC6H4O)P(micro-NtBu)}2)2]ClO4 (10) were obtained, respectively, from 1:1 and 2:1 stoichiometric reactions between 1a and [Au(SMe2)2]ClO4. Molecular structures of complexes 4, 6, 7, 8 and 9 are confirmed by single-crystal X-ray diffraction studies. Interestingly, the crystal structure of the tetra-nuclear AuI macrocycle 9 reveals the encapsulation of one ClO4- anion inside the bowl shaped macrocyclic cavity through weak Au...O and C-H...O interactions.
This paper describes the synthesis of a novel pyridine embedded 1,2,3-triazolylphosphine and its ... more This paper describes the synthesis of a novel pyridine embedded 1,2,3-triazolylphosphine and its group 11 metal chemistry.
This paper describes the synthesis of a novel 2,2′-bipyridine bridged bisphosphine and its doubly... more This paper describes the synthesis of a novel 2,2′-bipyridine bridged bisphosphine and its doubly B ← N bridged derivatives. The doubly B ← N bridged bisphosphine-chalcogenides exhibit excellent photophysical properties.
The synthesis and structural studies of palladium(II) complexes of sterically demanding mono‐phos... more The synthesis and structural studies of palladium(II) complexes of sterically demanding mono‐phosphine Ar*PPh2 (1) (Ar*=2,6‐dibenzhydryl‐4‐methylphenyl) are described. The reactions of 1 with [Pd(COD)Cl2] and [Pd(η3‐C3H5)Cl]2 in 2 : 1 molar ratios afforded mononuclear complexes trans‐[PdCl2{(PPh2Ar*)‐κ1‐P}2] (2) and [Pd(η3‐C3H5)Cl{(PPh2Ar*)‐κ1‐P}] (3), respectively. Both the complexes have been fully characterized through NMR spectroscopy, elemental analyses, and single‐crystal X‐ray analysis. The molecular structures of 2 and 3 showed C−H⋅⋅⋅π interactions between methine hydrogen of one of the Ph2CH groups with the centroid of one of the phenyl rings of the PPh2 group. Complex 2 also showed intramolecular π⋅⋅⋅π stacking interactions between the phenyl rings of Ph2CH and PPh2 groups. In addition, complex 2 also showed C−H⋅⋅⋅Pd anagostic interaction between the methine hydrogen of one of the Ph2CH groups and the palladium center. The palladium complex 2 is found to be an efficient ca...
Transition metal chemistry of [Ar*N(CH2PPh2)2] (1) derived from the sterically demanding backbone... more Transition metal chemistry of [Ar*N(CH2PPh2)2] (1) derived from the sterically demanding backbone 2,6‐dibenzhydryl‐4‐methylphenyl core is described. The reactions of 1 with 30 % aq. H2O2 and S8 afforded bischalcogenides [Ar*N(CH2P(O)Ph2)2] (2) and [Ar*N(CH2P(S)Ph2)2] (3), respectively. Treatment of 1 with [M(COD)Cl2] (M=Pd, Pt) in 1 : 1 molar ratios produced chelate complexes cis‐[MCl2{Ar*N(CH2PPh2)2}‐κ2‐P,P] (4, M=Pd; 5, M=Pt), whereas similar reaction between 1 and [Pd(η3‐C3H5)Cl]2 afforded dinuclear complex [{Pd(η3‐C3H5)Cl}2{Ar*N(CH2PPh2)2}‐κ1‐P,P] (6). The reaction of 1 with [Ru(η5‐C5H5)Cl(PPh3)2] in 1 : 1 ratio yielded [{Ru(η5‐C5H5)Cl}{Ar*N(CH2PPh2)2}‐κ2‐P,P] (7). Treatment of 1 with [M(C5H11N)2(CO)4] (M=Mo, W) in 1 : 1 molar ratios afforded cis‐[M(CO)4{Ar*N(CH2PPh2)2}‐κ2‐P,P] (8, M=Mo; 9, M=W). The reaction of 1 with copper(I) halides in 1 : 1 molar ratios produced [Cu(μ2‐X)]2 dinuclear complexes [{Cu(μ2‐X)}2{Ar*N(CH2PPh2)2}2‐κ2‐P,P}] [10, X=Cl; 11, X=Br; and 12, X=I]. Most of...
Abstract The upsurge in interest in pincer chemistry is because of their remarkable success in ho... more Abstract The upsurge in interest in pincer chemistry is because of their remarkable success in homogeneous catalysis for challenging organic transformations. Several groups have contributed significantly to the development of pincer ligands, their metal chemistry, and various applications. This chapter summarizes the synthesis of two types of pincers, viz, bisphosphomides and 1,2-phenylenediamine based PBP type ligands, their transition metal complexes, and catalytic applications.
This short review describes the recent developments in organophosphorus–chalcogen and organophosp... more This short review describes the recent developments in organophosphorus–chalcogen and organophosphorus–pincer macrocycles and their metal complexes with emphasis on synthetic methodologies.
This paper describes the synthesis and the copper(i), silver(i) and gold(i) complexes of a novel ... more This paper describes the synthesis and the copper(i), silver(i) and gold(i) complexes of a novel large bite angle bisphosphine {(C6H4(PhC2N3)PiPr2)2-p}.
In an attempt to establish the structures of the product formed in the reaction of PdCl2 and diph... more In an attempt to establish the structures of the product formed in the reaction of PdCl2 and diphenylacetylene in polar organic solvents, the reactions were carried out in alcohols, acetonitrile and tetrahydrofuran at room temperature. The reactions in protic solvents such as primary and secondary alcohols resulted in the cyclic dimerization of diphenylacetylene to yield the corresponding dimeric endo‐4‐alkoxy‐π‐1,2,3,4‐tetraphenylcyclobutenypalladium(II) chloride complexes 1–4 in good yields. In these complexes the tetraphenylcyclobutenyl moieties are coordinated to palladium atoms in η3‐mode and are bridged by two chlorides as confirmed by the single crystal X‐ray analysis of complexes 1, 2 and 4. In all these complexes, the coordination of cyclobutenyl moieties to palladium atoms are similar but a marked difference was observed for the Pd2Cl2 core which is planar in complex 1 but puckered in complexes 2 and 4 resulting in shorter Pd⋅⋅⋅Pd distances. The same reaction under solvent...
Dalton transactions (Cambridge, England : 2003), Jan 22, 2016
A new terpyridine-diphos hybrid ligand [4'-{p-(Ph2P)2NC6H4}-2,2':6'2''-terpy]... more A new terpyridine-diphos hybrid ligand [4'-{p-(Ph2P)2NC6H4}-2,2':6'2''-terpy] (1) and its Ru(II), Pd(II), Au(I) and Zn(II) complexes are described. Preliminary studies on absorption and emission properties are also reported.
Journal of Electron Spectroscopy and Related Phenomena, 1990
Journal of Electron Spectroscopy and Related Phenomena, 53 (1990) 119127 119 Elsevier Science Pub... more Journal of Electron Spectroscopy and Related Phenomena, 53 (1990) 119127 119 Elsevier Science Publishers BV, Amsterdam ELECTRONIC STRUCTURES OF RN(PX2)2 (R=CH3 OR C6H6; X=Cl, OCH3 OR OC6H6) LIGANDS: AN ULTRAVIOLET PHOTOELECTRON ...
ABSTRACT Graphical abstract The photophysical properties of triphenylphosphole-chalcogenides is d... more ABSTRACT Graphical abstract The photophysical properties of triphenylphosphole-chalcogenides is described.
Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(micro-NtBu)}2 (1a-1... more Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(micro-NtBu)}2 (1a-1d) produce binuclear gold(I) complexes of the type, [ClAu{RP(micro-NtBu)}2AuCl] (2 R=OC6H4OMe-o, 3R=OCH2CH2OMe, 4R=NEt2, 5R=NHtBu) in quantitative yield. A similar reaction between cis-{(o-MeOC6H4O)P(micro-NtBu)}2 (1a) and [AuCl(SMe2)] in a 1:1 molar ratio afforded the mono-nuclear complex [ClAu{(o-MeOC6H4O)P(micro-NtBu)}2] (6). Addition of two equivalents of CuX (X=Br, I) to the chloro derivative 2 leads to the formation of bromo, [BrAu{(o-MeOC6H4O)P(micro-NtBu)}2AuBr] (7), and iodo, [IAu{(o-MeOC6H4O)P(micro-NtBu)}2AuI] (8), derivatives through halogen exchange reactions. A tetranuclear gold(I) macrocycle [Au{(o-MeOC6H4O)P(micro-NtBu)}2]4(ClO4)4 (9) and a mononuclear gold(I) complex [Au({(o-MeOC6H4O)P(micro-NtBu)}2)2]ClO4 (10) were obtained, respectively, from 1:1 and 2:1 stoichiometric reactions between 1a and [Au(SMe2)2]ClO4. Molecular structures of complexes 4, 6, 7, 8 and 9 are confirmed by single-crystal X-ray diffraction studies. Interestingly, the crystal structure of the tetra-nuclear AuI macrocycle 9 reveals the encapsulation of one ClO4- anion inside the bowl shaped macrocyclic cavity through weak Au...O and C-H...O interactions.
This paper describes the synthesis of a novel pyridine embedded 1,2,3-triazolylphosphine and its ... more This paper describes the synthesis of a novel pyridine embedded 1,2,3-triazolylphosphine and its group 11 metal chemistry.
This paper describes the synthesis of a novel 2,2′-bipyridine bridged bisphosphine and its doubly... more This paper describes the synthesis of a novel 2,2′-bipyridine bridged bisphosphine and its doubly B ← N bridged derivatives. The doubly B ← N bridged bisphosphine-chalcogenides exhibit excellent photophysical properties.
The synthesis and structural studies of palladium(II) complexes of sterically demanding mono‐phos... more The synthesis and structural studies of palladium(II) complexes of sterically demanding mono‐phosphine Ar*PPh2 (1) (Ar*=2,6‐dibenzhydryl‐4‐methylphenyl) are described. The reactions of 1 with [Pd(COD)Cl2] and [Pd(η3‐C3H5)Cl]2 in 2 : 1 molar ratios afforded mononuclear complexes trans‐[PdCl2{(PPh2Ar*)‐κ1‐P}2] (2) and [Pd(η3‐C3H5)Cl{(PPh2Ar*)‐κ1‐P}] (3), respectively. Both the complexes have been fully characterized through NMR spectroscopy, elemental analyses, and single‐crystal X‐ray analysis. The molecular structures of 2 and 3 showed C−H⋅⋅⋅π interactions between methine hydrogen of one of the Ph2CH groups with the centroid of one of the phenyl rings of the PPh2 group. Complex 2 also showed intramolecular π⋅⋅⋅π stacking interactions between the phenyl rings of Ph2CH and PPh2 groups. In addition, complex 2 also showed C−H⋅⋅⋅Pd anagostic interaction between the methine hydrogen of one of the Ph2CH groups and the palladium center. The palladium complex 2 is found to be an efficient ca...
Transition metal chemistry of [Ar*N(CH2PPh2)2] (1) derived from the sterically demanding backbone... more Transition metal chemistry of [Ar*N(CH2PPh2)2] (1) derived from the sterically demanding backbone 2,6‐dibenzhydryl‐4‐methylphenyl core is described. The reactions of 1 with 30 % aq. H2O2 and S8 afforded bischalcogenides [Ar*N(CH2P(O)Ph2)2] (2) and [Ar*N(CH2P(S)Ph2)2] (3), respectively. Treatment of 1 with [M(COD)Cl2] (M=Pd, Pt) in 1 : 1 molar ratios produced chelate complexes cis‐[MCl2{Ar*N(CH2PPh2)2}‐κ2‐P,P] (4, M=Pd; 5, M=Pt), whereas similar reaction between 1 and [Pd(η3‐C3H5)Cl]2 afforded dinuclear complex [{Pd(η3‐C3H5)Cl}2{Ar*N(CH2PPh2)2}‐κ1‐P,P] (6). The reaction of 1 with [Ru(η5‐C5H5)Cl(PPh3)2] in 1 : 1 ratio yielded [{Ru(η5‐C5H5)Cl}{Ar*N(CH2PPh2)2}‐κ2‐P,P] (7). Treatment of 1 with [M(C5H11N)2(CO)4] (M=Mo, W) in 1 : 1 molar ratios afforded cis‐[M(CO)4{Ar*N(CH2PPh2)2}‐κ2‐P,P] (8, M=Mo; 9, M=W). The reaction of 1 with copper(I) halides in 1 : 1 molar ratios produced [Cu(μ2‐X)]2 dinuclear complexes [{Cu(μ2‐X)}2{Ar*N(CH2PPh2)2}2‐κ2‐P,P}] [10, X=Cl; 11, X=Br; and 12, X=I]. Most of...
Abstract The upsurge in interest in pincer chemistry is because of their remarkable success in ho... more Abstract The upsurge in interest in pincer chemistry is because of their remarkable success in homogeneous catalysis for challenging organic transformations. Several groups have contributed significantly to the development of pincer ligands, their metal chemistry, and various applications. This chapter summarizes the synthesis of two types of pincers, viz, bisphosphomides and 1,2-phenylenediamine based PBP type ligands, their transition metal complexes, and catalytic applications.
This short review describes the recent developments in organophosphorus–chalcogen and organophosp... more This short review describes the recent developments in organophosphorus–chalcogen and organophosphorus–pincer macrocycles and their metal complexes with emphasis on synthetic methodologies.
This paper describes the synthesis and the copper(i), silver(i) and gold(i) complexes of a novel ... more This paper describes the synthesis and the copper(i), silver(i) and gold(i) complexes of a novel large bite angle bisphosphine {(C6H4(PhC2N3)PiPr2)2-p}.
In an attempt to establish the structures of the product formed in the reaction of PdCl2 and diph... more In an attempt to establish the structures of the product formed in the reaction of PdCl2 and diphenylacetylene in polar organic solvents, the reactions were carried out in alcohols, acetonitrile and tetrahydrofuran at room temperature. The reactions in protic solvents such as primary and secondary alcohols resulted in the cyclic dimerization of diphenylacetylene to yield the corresponding dimeric endo‐4‐alkoxy‐π‐1,2,3,4‐tetraphenylcyclobutenypalladium(II) chloride complexes 1–4 in good yields. In these complexes the tetraphenylcyclobutenyl moieties are coordinated to palladium atoms in η3‐mode and are bridged by two chlorides as confirmed by the single crystal X‐ray analysis of complexes 1, 2 and 4. In all these complexes, the coordination of cyclobutenyl moieties to palladium atoms are similar but a marked difference was observed for the Pd2Cl2 core which is planar in complex 1 but puckered in complexes 2 and 4 resulting in shorter Pd⋅⋅⋅Pd distances. The same reaction under solvent...
Dalton transactions (Cambridge, England : 2003), Jan 22, 2016
A new terpyridine-diphos hybrid ligand [4'-{p-(Ph2P)2NC6H4}-2,2':6'2''-terpy]... more A new terpyridine-diphos hybrid ligand [4'-{p-(Ph2P)2NC6H4}-2,2':6'2''-terpy] (1) and its Ru(II), Pd(II), Au(I) and Zn(II) complexes are described. Preliminary studies on absorption and emission properties are also reported.
Journal of Electron Spectroscopy and Related Phenomena, 1990
Journal of Electron Spectroscopy and Related Phenomena, 53 (1990) 119127 119 Elsevier Science Pub... more Journal of Electron Spectroscopy and Related Phenomena, 53 (1990) 119127 119 Elsevier Science Publishers BV, Amsterdam ELECTRONIC STRUCTURES OF RN(PX2)2 (R=CH3 OR C6H6; X=Cl, OCH3 OR OC6H6) LIGANDS: AN ULTRAVIOLET PHOTOELECTRON ...
Uploads
Papers by Maravanji Balakrishna