Heterodifunctional ligands derived from monooxidized bis(phosphino)amines. Synthesis and transition metal (molybdenum(O), tungsten(O), rhodium(I), palladium(II), and platinum(II)) complexes of (diphenylphosphino)(diphenylphosphinothiolyl)- and (diphenylphosphino)(diphenylphosphinoselenoyl)phenylamine, Ph2PN(Ph)P(E)Ph2 (E = S, Se). Crystal and molecular structure of the Pt(II) complex [Cl2Pt(PPh2N(Ph)P(S)Ph2].cntdot.H2O

Balakrishna, Maravanji S.; Klein, Rita; Uhlenbrock, Stephen; Pinkerton, A. Alan; Cavell, Ronald G.

doi:10.1021/ic00077a005

Cited by 89 publications

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“…The extremely strong coupling with the P atom of the phosphine ligand ( 2 J PP = 327.5 Hz) can only be rationalized in the context of a trans arrangement between P A and PPh 3 [13][14][15][27][28][29][30][31]. The oxidized P(V) atom (P X ) of the bidentate ligand is not directly coordinated to the metal centre, thus coupling with 103 Rh is weak ( 3 J RhP = 3.7 Hz), as expected [23,32,33]. Coupling with P A ( 2 J PP = 52.8) and PPh 3 ( 3 J PP = 41.3 Hz) gives rise to a ddd-peak (d P = 68.9).…”

Section: Resultsmentioning

confidence: 98%

Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Chatziapostolou¹,

Vallianatou²,

Grigoropoulos³

et al. 2007

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 98%

Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Chatziapostolou¹,

Vallianatou²,

Grigoropoulos³

et al. 2007

Journal of Organometallic Chemistry

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“…The carbonylation reactions of alcohol were carried out in a 100 cm 3 teflon coated high pressure reactor (HR-100 Berghof, Germany) fitted with a pressure gauge and the reaction products were analyzed by GC (Chemito 8510, FID). The ligands (C 6 H 5 ) 2 PCH 2 P(Se)(C 6 H 5 ) 2 and (C 6 H 5 ) 2 PN(CH 3 )P(Se)-(C 6 H 5 ) 2 were prepared by the literature methods [39,40]. The starting complex [Rh(CO) 2 Cl] 2 was prepared by known method [41].…”

Section: General Proceduresmentioning

confidence: 99%

Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

Dutta

Woollins

Slawin

et al. 2006

Journal of Organometallic Chemistry

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“…1 widely conceived as inorganic analogues of the more familar -diketonate ligands, most notably acetylacetonate (acac). Only recently have the monochalcogenides Ph 2 PNHP(E)Ph 2 (E ) S, Se) been described 24 although Cavell has reported 25 the related ligands Ph 2 PN(Ph)P(E)Ph 2 (E ) S, Se). To further develop our understanding of these ligand systems, we sought to prepare the ligand Ph 2 PNHP(O)Ph 2 (hereafter abbreviated HL) containing both a "soft" and a "hard" donor atom.…”

Section: Introductionmentioning

confidence: 99%

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

et al. 1996

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The noncomplexed ligand Ph 2 PNHP(O)Ph 2 (HL) has been prepared, for the first time, from Ph 2 PNHPPh 2 (dppa) and H 2 O 2 in moderate yield. On further treatment with H 2 O 2 the phosphine oxide Ph 2 P(O)NHP(O)Ph 2 (1) can be formed. Reaction of [MCl 2 (COD)] (M ) Pt or Pd; COD ) cycloocta-1,5-diene) with 2 molar equiv of HL affords [MCl 2 (HL) 2 ] (4, 5) in which both ligands are monodentate P-bound. The analogous dibromo and diiodo derivatives [MX 2 (HL) 2 ] (6-9) were prepared from either [MX 2 (COD)] (M ) Pt or Pd; X ) Br or I) and HL or treatment of [MCl 2 (HL) 2 ] with an excess of NaI. Facile base deprotonation of the amine proton in 4 or 5 affords a new class of metallacycles [M(L) 2 ] [L -) Ph 2 PNP(O)Ph 2 -] (10, 11) incorporating two five-membered M-P-N-P-O rings. Compound 10 was independently made from [Pt(CH 3 ) 2 (COD)] and 2 equiv of HL in toluene at ambient temperature whereas the reaction of [Pt(CH 3 )Cl(COD)] with 2 equiv of HL affords solely trans-[Pt-(CH 3 )Cl(HL) 2 ] (13). Protonation of the neutral compound 10 with HCl in ethanol regenerates the ring-opened cis complex 4. In contrast, addition of HBF 4 ‚OEt 2 to 10 (or 11) results in exclusive protonation at the nitrogen atom of the chelating ligands to give cis-[M{Ph 2 PNHP(O)Ph 2 -P,O} 2 ][BF 4 ] 2 (15, 16); both chelate rings remain intact. The dicationic compounds 15, 16 can also be synthesized from 4, 5 in dichloromethane using Ag[BF 4 ] as a chloride abstractor. All new compounds described have been characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analyses. The molecular structures of Ph 2 PNHP(O)Ph 2 , cis-[PtBr 2 {Ph 2 PNHP(O)Ph 2 -P} 2 ], cis-[Pt{Ph 2 PNP(O)Ph 2 -P,O} 2 ], trans-[Pt(CH 3 )Cl{Ph 2 PNHP(O)Ph 2 -P} 2 ] and cis-[Pt{Ph 2 PNHP(O)Ph 2 -P,O} 2 ][BF 4 ] 2 have been determined by single-crystal X-ray diffraction. Crystals of HL are triclinic, space group P1 h, with a ) 10.410(2) Å, b ) 12.083(2) Å, c ) 9.036(4) Å, R ) 103.05(2)°, ) 99.09-(2)°, γ ) 72.98(1)°, V ) 1054 Å 3 , and Z ) 2. The final R and R w values were 0.061 and 0.047, respectively. Crystals of 6 are triclinic, space group P1 h, with a ) 13.113(4) Å, b ) 15.996(4) Å, c ) 13.011(4) Å, R ) 102.65(3)°, ) 117.39(2)°, γ ) 101.03(2)°, V ) 2225 Å 3 , and Z ) 2. The final R and R w values were 0.039 and 0.031, respectively. Crystals of 10 are monoclinic, space group P2 1 /a, with a ) 17.600(13) Å, b ) 13.498-(10) Å, c ) 18.641(9) Å, ) 105.13(1)°, V ) 4274 Å 3 , and Z ) 4. The final R and R w values were 0.041 and 0.036, respectively. Crystals of 13 are triclinic, space group P1 h, with a ) 14.686(2) Å, b ) 18.735(2) Å, c ) 9.018(3) Å, R ) 91.71(2)°, ) 102.27(2)°, γ ) 68.54(1)°, V ) 2253 Å 3 , and Z ) 2. The final R and R w values were 0.041 and 0.044, respectively. Crystals of 15 are orthorhombic, space group P2 1 2 1 2, with a ) 14.100(2) Å, b ) 19.002(1) Å, c ) 9.145(2) Å, V ) 2450 Å 3 , and Z ) 2. The final R and R w values were 0.052 and 0.057, respectively. The P-bound monodentate complexes contain ligands with similar...

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Cited by 89 publications

References 1 publication

Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

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Cited by 89 publications

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Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Synthesis and characterization of new RhI complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph2PNHP(O)Ph2

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Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂