Heterobifunctional Phosphorus-Nitrogen Compounds: Iminophosphoranophosphines and Their Complexes

Cavell, Ronald G.; Reed, Robert W.; Katti, Kattesh V.; Balakrishna, Maravanji S.; Collins, Paul W.; Mozol, Vivian; Bartz, I.

doi:10.1080/10426509308032345

Cited by 10 publications

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“…Oxidation of one phosphine center produces a large chemical shift change with creation of the P V center (which is deshielded by 20−60 ppm depending om the imine substituent) but leaves the chemical shift of the P III center relatively unaffected. This is in contrast to the behavior of dppm and the amine-bis(phosphine) analogs wherein both the P III and the P V signals shift markedly on imine formation at one center. − …”

Section: Resultsmentioning

confidence: 66%

“…We have previously described a number of phosphoranimino−phosphine ligands obtained by Staudinger oxidation of bis(phosphines) and the metal complexes derived from these versatile ligands. − It was of interest to explore the related chemistry of 1,2-bis(diphenylphosphino)benzene ( 1 ) because of the effects which could arise in such a case from constraining the two phosphine substituents to a cis orientation on the phenyl backbone. Beneficial effects which might be introduced by the aromatic character of the backbone could also be of interest.…”

Section: Introductionmentioning

confidence: 99%

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Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphosphorano)-2-(diphenylphosphino)benzene and Its Rhodium(I) Complex: 1-Ph₂PN(SiMe₃)C₆H₄-2-(Ph₂P)Rh(CO)Cl

1996

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Selective azide mono-oxidation of o-bis(phosphines) such as o-bis(diphenylphosphino)benzene and other bis(phosphines) with cis-substituents on a rigid backbone such as an ethylene structure occurs as the result of the steric control exerted during the azide oxidation (Staudinger) reaction process. The azides used were the trimethylsilyl, 4-cyanotetrafluorophenyl, benzyl, and diphenoxyphosphonyl azides. The prototypical ligand 1-Ph(2)P=N(SiMe(3))-2-(Ph(2)P)C(6)H(4), 2, has been structurally characterized. Crystal data for 2: crystal dimensions, 0.38 x 0.38 x 0.57 mm; space group, monoclinic, P2(1)/c, (No. 14); a = 11.093(5) Å, b = 14.898(5) Å, c = 18.811(2) Å, beta = 102.76(2) degrees, V = 3031 Å(3), Z = 4. Final R, R(w) and GOF values were 0.068, 0.074, and 1.92 respectively. The P=N-SiMe(3) angle was wide, 152.7(3) degrees, and the P=N bond length short (1.529(5) Å) relative to arylated iminophosphoranes but in keeping with the trends for silylated analogs. The iminophosphorane center can be selectively transformed with other agents in a Wittig type reaction converting the azides to the monooxide, monosulfide, etc. The iminophosphoranophosphines are also good complexing agents and the Rh(I) complex derived from 2, 1-Ph(2)P=N(SiMe(3))-C(6)H(4)-2-(Ph(2)P)Rh(CO)Cl, 15 was structurally characterized. Crystal data for 15: crystal dimensions, 0.32 x 0.44 x 0.66 mm; space group, monoclinic, P2(1)/c (No. 14); a = 13.793(3) Å, b = 12.622(11) Å, c = 20.436(6) Å, beta = 105.93(2) degrees, V = 3421.2 Å(3), Z = 4. Final R, R(w), and GOF values were 0.064, 0.061, and 1.45 respectively. The complex shows typical square planar geometry about Rh, a cis phosphine-CO relationship, and no exceptional steric crowding of the coordination site.

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Section: Resultsmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 99%

Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphosphorano)-2-(diphenylphosphino)benzene and Its Rhodium(I) Complex: 1-Ph₂PN(SiMe₃)C₆H₄-2-(Ph₂P)Rh(CO)Cl

1996

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“…The first one is the Staudinger reaction, 13,14 which relies on the addition of an azide to a phosphine (eq 1). This method has been used with great success by Cavell et al (R ) SiMe 3 ) 7,11,15 and more recently by Gimeno et al (R ) P(X)(OR) 2 ). 9 Indeed, with 1 equiv of azide, the mixed ligands are obtained in high yields.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of New Mixed Phosphine∼Iminophosphorane Bidentate Ligands and Their Coordination to Group 10 Metal Centers

et al. 2005

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The selective monobromation of a symmetrical bidentate diphosphine (dppm = bis-diphenylphosphinomethane) yielding a highly reactive intermediate, 2 (P∼PBr+·Br-), is reported. Two methods of trapping were devised to produce mixed phosphine−aminophosphonium salts 3 (P∼PNHR+·Br-). The first method relies on the reaction of 2 with 2 equiv of primary amine to give 3a−c (P∼PNHR+·Br-, R = p-Me-Bn, p-MeO-Bn, Ph). The second method utilizes 1 equiv of primary amine and DABCO as trapping agent to give 3a−e (P∼PNHR+·Br-, R = p-Me-Bn, p-MeO-Bn, Ph, nBu, α(+)-Me-benzyl). These salts were then deprotonated quantitatively to yield the desired new phosphine−iminophosphorane ligands 4a−e (P∼PNR). This simple strategy allows for a wide variation of the R substituent at the nitrogen donor group (R = alkyl, aryl, benzyl). In particular, the optically pure ligand 4e (R = α(+)-Me-benzyl) was obtained in one pot from commercially available α(+)-Me-benzylamine. Reaction of 4 with Pd(COD)Cl2 affords the complexes 5 via coordination to Pd(II) centers and revealed the chelating behavior of these ligands. X-ray crystal structures of 5a (presented in ESI), 5c, and 5e are reported. Complexes of platinum(II), 6c and 6e, were also synthesized and characterized crystallographically. The complex of nickel(II), 7a, adopts a tetrahedral geometry as shown by X-ray analysis and consistent with a lack of NMR signal.

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“…The reagents NH(PPh,),, NH(SPPh,), and Na[N(SPPh,),] were prepared by literature methods. 5 9 6 The P-{ H} (1 09.4…”

Section: Methodsmentioning

confidence: 99%

Preparation and characterisation of [Pt{N(SePPh₂)₂-Se,Se′}(PR₃)₂]Cl (R = alkyl or aryl); crystal structure of [Pd{Ph₂PNP(Se)Ph₂-P,Se}{N(SePPh₂)₂-Se,Se′}]·0.5EtOH·0.3CH₂Cl₂

Bhattacharyya¹,

Slawin²,

Williams³

et al. 1995

J. Chem. Soc., Dalton Trans.

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Heterobifunctional Phosphorus-Nitrogen Compounds: Iminophosphoranophosphines and Their Complexes

Cited by 10 publications

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Synthesis of New Mixed Phosphine∼Iminophosphorane Bidentate Ligands and Their Coordination to Group 10 Metal Centers

Preparation and characterisation of [Pt{N(SePPh₂)₂-Se,Se′}(PR₃)₂]Cl (R = alkyl or aryl); crystal structure of [Pd{Ph₂PNP(Se)Ph₂-P,Se}{N(SePPh₂)₂-Se,Se′}]·0.5EtOH·0.3CH₂Cl₂

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Heterobifunctional Phosphorus-Nitrogen Compounds: Iminophosphoranophosphines and Their Complexes

Cited by 10 publications

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Synthesis of New Mixed Phosphine∼Iminophosphorane Bidentate Ligands and Their Coordination to Group 10 Metal Centers

Preparation and characterisation of [Pt{N(SePPh2)2-Se,Se′}(PR3)2]Cl (R = alkyl or aryl); crystal structure of [Pd{Ph2PNP(Se)Ph2-P,Se}{N(SePPh2)2-Se,Se′}]·0.5EtOH·0.3CH2Cl2

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Preparation and characterisation of [Pt{N(SePPh₂)₂-Se,Se′}(PR₃)₂]Cl (R = alkyl or aryl); crystal structure of [Pd{Ph₂PNP(Se)Ph₂-P,Se}{N(SePPh₂)₂-Se,Se′}]·0.5EtOH·0.3CH₂Cl₂