31P and 195Pt NMR characteristics of new binuclear complexes of [Pt2X4](PR3)2] cis/trans isomers and of mononuclear analogs

Al‐Najjar, Ibrahim M.

doi:10.1016/s0020-1693(00)84701-5

Cited by 45 publications

(28 citation statements)

References 17 publications

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“…The low 1 J Pt,P value suggests a trans geometry for complex 7. [34] The EI mass spectrum of complex 7 shows the molecular ion peak at m/z 1838.01 [ mass spectrum of complex 10 are in accordance with the proposed structure, which was further confirmed by singlecrystal X-ray diffraction studies.…”

Section: Synthesis Of the Ligand And Chalcogen Derivativessupporting

confidence: 68%

The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

2007

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The iminophosphorane‐phosphane ligand Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2 (1) has been synthesized by partial imination of bis[2‐(diphenylphosphanyl)phenyl] ether (DPEphos) with phosphoryl azide (PhO)2P(O)N3. A similar reaction in a 1:2 stoichiometry affords the bis(iminophosphorane) O{C6H4PPh2=NP(O)(OPh)2}2 (2). The chalcogen derivatives O{C6H4P(E)Ph2}2 [E = S (3) and Se (4)] and Ph2P(E)C6H4OC6H4PPh2=NP(O)(OPh)2 [E = S (5) and Se (6)] are also synthesized by treating DPEphos and 1 with elemental sulfur and selenium, respectively. The mononuclear complexestrans‐[MCl2{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2][M = Pt (7) Pd (8)] and trans‐[Rh(CO)Cl{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2] (12) are prepared by the reaction of 1 with [Pt(COD)Cl2], [Pd(COD)Cl2], and [{Rh(CO)2Cl}2], respectively. Treatment of 1 with [Pd2(dba3)] (dba = dibenzylideneacetone) affords the mononuclear complex [Pd0{κ2‐P,O‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}2] (9) in which ligand 1 coordinates through its P and O centers in a κ2‐P,O chelating fashion. The monocoordinated AuI complex [AuCl{κ1‐P‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}] (10) has been prepared by the reaction of 1 and [AuCl(SMe2)] and its structure has been confirmed by X‐ray crystallography. The reaction of 1 with [{Rh(COD)Cl}2] in the presence of AgOTf affords the cationic RhI complex cis‐[Rh(COD){κ2‐P,O‐Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2}][OTf] (11). The catalytic activity of the Pd0 complex 9 has been investigated in Suzuki cross‐coupling reactions. Homogeneous catalytic hydrogenation of olefins has also been studied using the cationic RhI complex 11.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Synthesis Of the Ligand And Chalcogen Derivativessupporting

confidence: 68%

The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

2007

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“…The 31 P NMR spectrum of 9 in CDCl 3 showed a sharp resonance at 15 [11]. The possible other isomer, having a trans-geometry, was not observed.…”

Section: Preparative Resultsmentioning

confidence: 86%

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Kreiter

Firet

Ruts

et al. 2006

Journal of Organometallic Chemistry

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The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino)methyl-functionalized triarylphosphanes of the general formula PPh 3 À n Ar n (Ar = 1-C 6 H 3 (CH 2 NMe 2 ) 2 -3,5 (NC(H)N), n = 1 (ligand 2) or n = 3 (ligand 4); Ar = 1-C 6 H 4 (CH 2 NMe 2 )-4 (NC(H)), n = 3 (ligand 7)) is described. These phosphanes were used for the construction of complexes of the form [AuCl(P)] and [PtCl 2 (P) 2 ]. In these complexes selective coordination of phosphorus to the metal ion is observed. The 31 P NMR data show the formation of cis-Pt complexes, even in the case of triarylphosphane 4, which features a tris{3,5-bis(dimethylamino)methyl} substitution pattern. The structure of the gold complex of mono-3,5-functionalized triarylphosphane 2 in the solid state shows a striking resemblance to the structure of the corresponding complex [AuCl(PPh 3 )]. The solid-state structure of the AuCl complex of tris-4-functionalized ligand 7 differs from that of [AuCl(PPh 3 )] in the sign of the torsion angles. The amine functionalities in this class of gold compounds could be reacted selectively with either acid (HCl, H 3 PO 4 ) to generate ammonium salts or with an alkylating agent (benzyl bromide) to afford benzyl ammonium salts, without the violation of the Au-P bond.

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“…Although all the compounds are stable in the solid state, 3 and 4 tend to decompose after 1-2 days in solution to yield trans-[(Cy 3 P) 2 PtX 2 ] and trans-[(Cy 3 P) 2 Pt(H)X] (X = Br, I), as indicated by 31 P{ 1 H} NMR spectroscopy. [22] In conclusion, the first platinum alane complexes are reported, which display an unsupported bond between a dblock and a p-block metal. From the structural data of trans-[(Cy 3 P) 2 PtÀAlCl 3 ] (2) the presence of a strong dative Pt-Al bond can be concluded.…”

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confidence: 83%

Interaction between d‐ and p‐Block Metals: Synthesis and Structure of Platinum–Alane Adducts

2007

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Dative bonds between transition metals and the archetypal Lewis acid BF 3 were proposed as early as 1966, [1] but were called into question 30 years later.[2] However, more recent work by Hill, [3] Parkin, [4] Bourissou, [5] and Rabinovich [6] and respective co-workers has demonstrated that borane complexes of the type [L n M À BR 3 ] [7] can be obtained from a range of late Lewis basic transition metals, and the nature of the dative metal-boron bond has been elucidated by experimental and computational studies. In addition, the metal-phosphine fragments {M(PCy 3 )} (M = Pd, Pt) have proven to act as versatile metal bases towards a range of coordinated boryl [8] and borylene ligands. [9] The heavier Group 13 elements are also known to form a variety of transition-metal complexes, in analogy to boron.[10]

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31P and 195Pt NMR characteristics of new binuclear complexes of [Pt2X4](PR3)2] cis/trans isomers and of mononuclear analogs

Cited by 45 publications

References 17 publications

The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Interaction between d‐ and p‐Block Metals: Synthesis and Structure of Platinum–Alane Adducts

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31P and 195Pt NMR characteristics of new binuclear complexes of [Pt2X4](PR3)2] cis/trans isomers and of mononuclear analogs

Cited by 45 publications

References 17 publications

The Iminophosphorane‐Phosphane Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

The Iminophosphorane‐Phosphane Ph2PC6H4OC6H4PPh2=NP(O)(OPh)2: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

Synthesis, coordination chemistry, and metal complex reactivity of (dimethylamino)methyl-substituted triarylphosphanes; X-ray study on [AuCl(PPh3−nArn)] (Ar=1-C6H3(CH2NMe2)2-3,5, n=1, 3; Ar=1-C6H4(CH2NMe2)-4, n=3)

Interaction between d‐ and p‐Block Metals: Synthesis and Structure of Platinum–Alane Adducts

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The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins

The Iminophosphorane‐Phosphane Ph₂PC₆H₄OC₆H₄PPh₂=NP(O)(OPh)₂: Synthesis, Reactivity, and Catalytic Activity in Suzuki Cross‐Coupling and the Homogeneous Hydrogenation of Olefins