A phosphorus-31 nuclear magnetic resonance study of tertiary phosphine complexes of platinum(II)

Grim, Samuel O.; Keiter, Richard L.; McFarlane, William

doi:10.1021/ic50052a015

Cited by 220 publications

(93 citation statements)

References 2 publications

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“…the 31P resonance moves to lower field on coordination), as has been observed in many monodentate and polydentate organophosphine complexes (8,9), thus corroborating phosphorus-to-metal bonding.…”

Section: The 31p Proton Decoupled F T Nrnr Spectra Of the Complexes [supporting

confidence: 74%

[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

Hoyano¹,

Peterson²

1976

Can. J. Chem.

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. Can. J. Chem. 54, 2697Chem. 54, (1976. A series of complexes [LM(C0)3X] (L = +zP(R2pz)3-z, RZPZ = pyrazolyl, or 3,5-dimethylpyrazolyl, x = 0-2; M = Mn, X = C1; M = Re, X = Br) and [(+2P(S)(R2pz))Re(CO), Br] were prepared by the reaction of the appropriate ligand with [M(CO),X] or [M(CO),X],, and were characterized by elemental analysis, solution molecular weight, and infrared, mass, and nmr spectroscopic data. The products are formed via tetracarbonyl intermediates, of which the phosphorus bonded derivative [(+2P(pz))Re(CO),Br] was isolated and characterized. The tricarbonyl complexes [LM(C0)3X] and [(+2P(S)(R2pz))Re(CO)3Br] adopt a cis-octahedral configuration, in which the ligands form four-, five-, or six-membered chelate structures, via (i) the P atom and the 2-N site of the pyrazolyl moiety, with +2P(R2p~)r (ii) the sulphur and 2-N atoms, with +2P(S)(R2pz), (iii) the 2-N atoms of two pyrazolyl rings, with + P ( R ,~Z )~, and (iv) the 2-N atoms of three pyrazolyl rings, resulting in a bicyclic system, with P(R2pz)3.The reactions of [CH3Re(CO)5] with +zP(R2pz)3-z require forcing conditions, resulting in the simultaneous elimination of carbon monoxide and methane, and yielding a variety of products, including tetracarbonyl, tricarbonyl, and ring-metalated species.

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Section: The 31p Proton Decoupled F T Nrnr Spectra Of the Complexes [supporting

confidence: 74%

[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

Hoyano¹,

Peterson²

1976

Can. J. Chem.

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“…For example, the magnitude of lJ(M-P) for complexes of tungsten(0) (8) and platinum(I1) (9) with the phosphines P&Ph,, (R = alkyl, Ph = 'Present address: Department of Chemistry and Chemical Engineering, Universityof Saskatchewan, Sakkatoon, Sask., Canada S7N OW0 whom all correspondence should be addressed phenyl) increases as n decreases but the opposite is true for some mercury(I1) complexes (10). From these results it has been concluded (8-10) that the magnitude of 1J(183W-3 lP) or 1J(195Pt-31P) increases with decreasing basicity whereas the 1J(199Hg-31P) values vary in the opposite manner.…”

Section: Introductionmentioning

confidence: 99%

The basicity of phosphines

Allman¹,

Goel²

1982

Can. J. Chem.

210

112

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The basicities of the triarylphosphines P(4-XC6H4)3 (X = Cl, F, H, CH3, CH3O, (CH3)2N), P(3-CH3C6H4)3, and P(2-CH3C6H7)3 as well as the trialkylphosphines P(t-Bu)3 and PCy3 have been measured by the nitromethane titration method. The range of basicity available by aryl substitution is very large, being pKa = 8.65 for X = (CH3)2N to 1.03 for X = Cl. The most basic phosphine is P(t-Bu)3 whose pKa = 11.40. The measured basicities correlate well with σp, [Formula: see text], and ν as well as with the lone pair ionisation potentials of the triarylphosphines. Generally the 1H, 31P, and 13C nmr spectral parameters of the free and protonated phosphines do not correlate well with pKa.

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“…While the tert-butyl groups in complex 5 cause the smallest P-Pt coupling constant, the diphenylamino groups in complex 8 are responsible for the largest P-Pt coupling constant. In general, the P-Pt coupling constants of the complexes increase with the electronegativity of the substituents on phosphorus, which increases the -acceptor character of the phosphines [Hill et al, 1983;Grim et al, 1967].…”

Section: Synthesis and Spectroscopic Properties Of Platinum Complexesmentioning

confidence: 99%

“…Therefore, compound 7, which possess the largest 1 J PPt coupling constant, display the shortest Pt-P bonds. This trend is expected since the electron-withdrawing substituents on the phosphorus atoms increase the d  d  interaction between the platinum and the phosphorus donor atoms [Grim et al, 1967]. On the other hand, this so-called backbonding would also increase the -bond character of the Pt-P bond by a synergistic effect [Grim et al, 1967].…”

mentioning

confidence: 99%

Platinum Metal Complexes of Carbaboranylphophines: Potential Anti Cancer Agents

Maulana

Loennecke

Hawkins

2010

Indones J Cancer Chemoprevent

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Polyhedral heteroboranes in particular dicarba-closo-dodecaboranes(12) and their organic derivatives have been the subject of intense research for over 40 years due to their unique chemical and physical properties. The initial attraction to dicarba-closododecaboranes(12) In the medicinal chemistry research, was a result of their high boron content and stability to catabolism, which are important criteria for cancer therapy, such as BNCT (boron neutron capture therapy) agents. The coordination compounds of the platinum group metals have also received large interest for their potential application as chemotherapeutic agents, since cis-diamminedichloroplatinum(II), cisplatin, has been reported to have capability as tumor inhibitor. Hence, applications can be envisioned for related cis platinum complexes. Complex of cis-rac-[PtCl2{1,2-(PRCl)2C2B10H10}] (R=Ph, t Bu, NEt2, NPh2) have been synthesized by employing known carbaborane based phosphine ligands of clorophoshino-closo-dodecaborane , with complex of cis-[PtCl2(COD)] (COD = 1,5-cyclooctadiene) in an N2-atmosphere. The obtained complexes possess expected structure configuration, namely cis-rac. The characterization of the complex has been carried out using 1 H, 31 P, 13 C and 11 B-NMR (Nuclear Magnetic Resonance), X-ray of single crystals, elemental analysis, IR (infra red) and mass spectroscopy (MS). The 31 P{ 1 H} NMR spectra of all the platinum complexes distinctly show the typical platinum satellites which are attributed to 31 P-195 Pt-coupling, in which the 31 P{ 1 H} NMR spectrum exhibits three lines with an intensity ratio of ca. 1:4:1. The structure of the platinum complexes consists of a slightly distorted square-planar coordination sphere, in which the platinum atom is bonded to two chlorides and two phosphorus atoms of the chelating carbaboranylphosphine. Thus the platinum atoms exhibit the coordination number four, which is preferred in platinum(II) complexes.

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A phosphorus-31 nuclear magnetic resonance study of tertiary phosphine complexes of platinum(II)

Cited by 220 publications

References 2 publications

[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

The basicity of phosphines

Platinum Metal Complexes of Carbaboranylphophines: Potential Anti Cancer Agents

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A phosphorus-31 nuclear magnetic resonance study of tertiary phosphine complexes of platinum(II)

Cited by 220 publications

References 2 publications

[LM(CO)3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

[LM(CO)3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

The basicity of phosphines

Platinum Metal Complexes of Carbaboranylphophines: Potential Anti Cancer Agents

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Product

Resources

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[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands

[LM(CO)_3,4X] complexes of manganese(I) and rhenium(I) with phosphino- and thiophosphinatopyrazole ligands