Iron(II), cobalt(II) and nickel(II) complexes of phosphorus-nitrogen ligands

Dahlhoff, W. V.; Dick, T. R.; Ford, G. H.; Nelson, S. M.

doi:10.1016/0022-1902(71)80617-6

Cited by 25 publications

(18 citation statements)

References 17 publications

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“…The N-coordination of diphenyl(2-pyridyl)phosphine to a metal ion results in a shift to higher frequencies in the IR absorptions of the pyridine ring by 15-30 cm −1 [239,240]. Based on this shift in IR absorptions, early studies [241,242] focused on dividing the metal complexes of diphenyl(2-pyridyl)phosphine into those in which the metal is essentially P-coordinated or N-coordinated.…”

Section: Silver(i) Complexes Of Pyridylphosphinesmentioning

confidence: 97%

Coordination complexes of silver(I) with tertiary phosphine and related ligands

Meijboom¹,

Bowen²,

Berners‐Price³

2009

Coordination Chemistry Reviews

144

120

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Section: Silver(i) Complexes Of Pyridylphosphinesmentioning

confidence: 97%

Coordination complexes of silver(I) with tertiary phosphine and related ligands

Meijboom¹,

Bowen²,

Berners‐Price³

2009

Coordination Chemistry Reviews

144

120

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“…Some efforts in coordination chemistry research have recently been directed towards the study of metal complexes of the hybrid hemilabile P-N- [5][6][7][8][9][10][11][12], P-O- [13,14] or P-S- [15][16][17] type ligands. This is due to their structural features, reactivity and catalytic properties resulting from the combination of a soft phosphine moiety with a hard oxygen-or nitrogen-donor functionality.…”

Section: Introductionmentioning

confidence: 99%

“…Some of these complexes display P-and N-chelation where the P-and N-donors of the ligands are simultaneously bonded to the same metal centre [5][6][7][8][9][10][11][12]. In this way they behave as hemilabile ligands with one arm, strongly bonded to the electron-rich transition metal centre and the other forming a weak bond with the metal, which can readily dissociate to generate a vacant site on the metal for the formation and/or stabilization of an intermediate species.…”

Section: Introductionmentioning

confidence: 99%

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<b>Synthesis and characterisation of some metal complexes of hybrid phosphorus-nitrogenligands: the crystal structure of 1-(diphenylphosphino)-2-(2-pyridyl)ethane cobalt(II) chloride</b>

Ndifon

Agwara

Hayashi

et al. 2008

Bull. Chem. Soc. Eth.

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ABSTRACT. Some iron(II), cobalt(II) and copper(II) complexes of the hybrid ligand 1-(diphenylphosphino)-2-(2-pyridyl)ethane (dppe) and diphenyl-2-pyridylphosphine (dppp) have been synthesised and characterised. Analyses suggest tetrahedral structures in which the metal atoms are bonded to two chlorine atoms and to both phosphorus and nitrogen atoms for 1-(diphenylphosphino)-2-(2-pyridyl)ethane on one hand and on the other hand, bonding is through the nitrogen atoms of two molecules of diphenyl-2-pyridylphosphine, which acts as a monodentate ligand. The crystal structure of 1-(diphenylphosphino)-2-(2-pyridyl)ethane cobalt(II) chloride shows a pseudo-tetrahedral structure in which the aminophosphine is bonded to the cobalt centre through both the phosphorus and nitrogen atoms, forming a 6-membered ring.

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“…The IR spectrum of complex 38 contained a C=O stretch at 1638 cm −1 consistent with the presence of an acyl group, 71 while the C=N stretches at 1573 and 1562 cm −1 indicated the pyridyl nitrogens were not coordinated to the platinum. 40,107,[134][135][136] In contrast, when the [PtClMe(P ′ P ′ )] complex (…”

Section: Reactions Of [Ptme(pp)]xmentioning

confidence: 99%

Late Transition Metal Complexes of Pyridyldiphosphines

Vaughan¹

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<p>This thesis provides an account of research into the properties of pyridyldiphosphines with o-xylene and m-xylene backbones. The coordination behaviour of the o-xylene based ligand with platinum, palladium, silver, rhodium and iridium metal centres has been studied, with an emphasis on whether the presence of the pyridyl rings affects the products formed. Platinum and palladium pincer complexes have been synthesised and the intermediates investigated. The formation of trimetallic complexes with these ligands acting as bridging ligands has also been explored. Two new pyridyldiphosphines, o-C₆H₄(CH₂PPy₂)₂ (3) and m-C₆H₄(CH₂PPy₂)₂ (4), and one known pyridyldiphosphine, PPy₂(CH₂)₃PPy₂ (5), have been synthesised via an improved method. Tris(2-pyridyl)phopshine was reacted with a lithium dispersion to give LiPPy₂, which was then reacted with the appropriate dichloride or dibromide compound to yield the desired ligand. The phosphine selenides of 3 and 4 were synthesised and the ¹J PSe values of 738 and 742 Hz indicated these ligands were less basic than PPh₃. While the ligands themselves were not water-soluble, protonation by a strong acid, such as HCl or H₂C(SO₂CF₃)₃, rendered them soluble in water. A series of [MX₂(PP)] complexes (where M = Pt, X = Cl, I, Me, Et, PP = 3, 5; M = Pd, X = Cl, Me PP = 3, 5) were synthesised. Complexes of 3 displayed dynamic behaviour in solution which was attributed to the backbone of the ligand inverting. When [PtMeCl(PP)] (27) was reacted with NaCH(SO₂CF₃)₂ no evidence for the coordination of the pyridyl nitrogens was observed. The synthesis of a series of unsymetrical [PtMeL(PP)]⁺ complexes enabled the comparison of the cis and trans influences of a range of ligands. The following cis influence series was compiled based on ³¹P NMR data of these complexes: Py ≈ Cl > SEt₂ > PTA > PPh₃. Reaction of 27 with NaCH(SO₂CF₃)₂ and carbon monoxide slowly formed an acyl complex, where the CO had inserted in the Pt–Me bond. The bis-chelated complexes [M(PP)₂] where M = Pt, Pd, and [Ag(PP)₂]⁺ were formed. In these complexes 3 acted as a diphosphine ligand and there was no evidence for any interaction between the pyridyl nitrogen atoms and the metal centre. Reaction of 3 with [Ir(COD)(μ-Cl)]₂ formed [IrCl(PP)(COD)] (42). When the chloride ligand in 42 was abstracted, the pyridyl nitrogens were able to interact with the iridium centre faciliating the isomerisation of the 1,2,5,6-ƞ⁴-COD ligand to a 1-к-4,5,6-ƞ³-C₈H₁₂ ligand. The X-ray crystal structure of [Ir(1-к-4,5,6-ƞ³-C₈H₁₂)(PPN)]BPh₄ (43) confirmed the P,P,N chelation mode of the ligand. In solution, 43 displayed hemilabile behaviour, with the pyridyl nitrogens exchanging at a rate faster than the NMR time scale at room temperature. The coordinated pyridyl nitrogen was able to be displaced by carbon monoxide to form [Ir(1-к-4,5,6-ƞ³-C₈H₁₂)(CO)(PP)]⁺. A series of [PtXY(μ-PP)]₂ complexes, where X = Y = Cl, Me, X = Cl, Y = Me and PP = 4, were formed initially when 4 was reacted with platinum(II) complexes. When heated, the dimers containing methyl ligands eliminated methane to form [PtX(PCP)] pincer complexes, X = Cl (49), Me (51). When the chloride ligand in 49 was abstracted no evidence of pyridyl nitrogen coordination was observed. Protonation of 49 did not yield a water-soluble pincer complex. The [PdCl₂(μ-PP)]₂ complex readily metallated when heated to give the pincer complex [PdCl(PCP)]. Given pyridyl nitrogen atoms are known to be good ligands for “hard” metal centres, the ability of the pyridyl nitrogens in 3 and 4 to coordinate to metal centres was investigated. While complexes with chloride ligands were found to form insoluble products, the synthesis of [(PtMe₂)₃(PP)], from the reaction of either 3 or [PtMe₂(PP)] (17) with dimethyl(hexa-1,5-diene)platinum, proceeded smoothly through a dimetallic intermediate. The same reactivity was observed in the synthesis of [(PtMe₂)₂PtMe(PCP)]. In contrast, the cationic heterotrimetallic complexes [{M(COD)}₂PtMe(PP)]²⁺ and [{M(COD)}₂PtMe(PCP)]²⁺, where M = Rh or Ir, were synthesised without the detection of any intermediates. However, dimetallic complexes were formed as part of a mixture when 17 or 51 was reacted with one equivalent of the appropriate metal complex.</p>

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Iron(II), cobalt(II) and nickel(II) complexes of phosphorus-nitrogen ligands

Cited by 25 publications

References 17 publications

Coordination complexes of silver(I) with tertiary phosphine and related ligands

Coordination complexes of silver(I) with tertiary phosphine and related ligands

<b>Synthesis and characterisation of some metal complexes of hybrid phosphorus-nitrogenligands: the crystal structure of 1-(diphenylphosphino)-2-(2-pyridyl)ethane cobalt(II) chloride</b>

Late Transition Metal Complexes of Pyridyldiphosphines

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