An acetone complex of platinum

Thayer, A. G.; Payne, Nicholas C.

doi:10.1107/s0108270186092478

Cited by 9 publications

(3 citation statements)

References 14 publications

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“…Although chloride is a much better ligand than SO 3 CF 3 −, the Me 3 Sn group has a considerably higher trans influence than methyl, and hence the systems are roughly analogous. Precedence for the stability of platinum−acetone complexes has been established by the structure of [PtMe(Me 2 CO)(PMe 2 Ph) 2 ]PF 6 …”

Section: Discussionmentioning

confidence: 99%

Rapid Reversible Oxidative Addition of Group 14−Halide Bonds to Platinum(II): Rates, Equilibria, and Bond Energies

Levy

Puddephatt

1997

J. Am. Chem. Soc.

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The reversible oxidative addition reactions of methyl(halogeno)tin and methyl(halogeno)germanium compounds to electron-rich platinum(II) complexes of the type [PtMe2(diimine)] have been studied. Complete kinetic and thermodynamic parameters have been obtained by VT 1H NMR for the reversible oxidative addition of Me3EX (E = Sn, X = Cl, Br, I) to [PtMe2(bpy- t bu2)] (bpy- t bu2 = 4,4‘-di-tert -butyl-2,2‘-bipyridyl) and related compounds, while partial data have been obtained for the reductive elimination of Me2SnCl2 from [PtClMe2(Me2SnCl)(bpy- t bu2)] and for the oxidative addition of Me3GeCl to [PtMe2(bpy- t bu2)]. UV−visible spectroscopic studies have also yielded equilibrium constants and ΔG° for the reversible oxidative addition reactions of Me3SnX (X = Cl, Br, I) to [PtMe2(diimine)]. Thermodynamic studies quantitatively establish the halogen effect on the oxidative addition reactions studied according to the favorability series I > Br > Cl. Kinetic studies clearly point to an SN2 mechanism for the reactions studied, and this is further supported by the observation of the cationic complex [PtMe2(Me3Sn)(bpy- t bu2){OC(CD3)2}]+ at low temperature in acetone-d 6. Extremely large second-order rate constants are observed for the oxidative addition of Sn−X bonds to dimethylplatinum(II) complexes, some being greater than 108 M-1 s-1, and it is established that rates follow the series Sn > Ge > Si > C and I > Br > Cl. Estimates have been made of the Pt−MMe3 bond dissociation energies for [PtXMe2(MMe3)(bpy- t bu2)], X = halide, and these are 233, 182, and 172 kJ mol-1 for M = Si, Ge, and Sn, respectively; the values are useful in rationalizing the chemistry of the Pt−M bonds.

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Section: Discussionmentioning

confidence: 99%

Rapid Reversible Oxidative Addition of Group 14−Halide Bonds to Platinum(II): Rates, Equilibria, and Bond Energies

Levy

Puddephatt

1997

J. Am. Chem. Soc.

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“…However, y;2-benzaldehyde complex 14 (C-O bond length 1.325(7) A) (24e, f) and tj2-benzophenone complex (Et3P)2- HaC^"/ \^CH3 show that electron-withdrawing substituents are not essential for r]2 coordination. Interestingly, acetone binds V to platinum(II) (30,32), as illustrated by 15 (eq 24). This can be rationalized by the lower metal electron density.…”

Section: Other Types Of Complexesmentioning

confidence: 99%

Aldehyde and ketone ligands in organometallic complexes and catalysis

Huang¹,

Gladysz²

1988

J. Chem. Educ.

115

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Aldehydes and ketones are two of the most important functional groups in organic chemistry. Their synthetic and mechanistic chemistry has been studied in detail (1). It has also been known for some time that aldehydes and ketones can serve as ligands in transition metal complexes (2-33). However, this area has not received a great deal of systematic study. Indeed, the frequent use of acetone as a reaction or recrystallization solvent has likely led to the occasional serendipitous synthesis of acetone complexes-or at least it has once in the authors' laboratory.There are numerous transition metal catalyzed reactions that involve aldehyde or ketone starting materials or intermediates (34-37). Two industrially important examples are given in Figure 1. Clearly, the systematic study of stable aldehyde and ketone complexes is necesary to provide in-Volume 65 Number 4

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“…We have extended our investigation on the effect of formyl group in ortho phenylethynylbenzaldehyde towards the complex formation by iron pentacarbonyl. It has been observed that h 2 form of bonding of the formyl group is preferred when the metallic part [M] is a d 10 ML 2 fragment (Pt(PR 3 ) 2 [16,17], Pd(PR 3 ) 2 [18], Ni(PR 3 ) 2 [19e21]) or a C 2v d 8 ML 4 fragment (Os(CO) 2 (PR 3 ) 2 [22], Ru(CO) 2 (PR 3 ) 2 [23,24], Fe(CO) 2 (PR 3 ) 2 [25]) while the h 1 form is preferred when [M] is a d 8 ML 3 fragment ( PtCl 2 (pyridine) [26,27], Pt þ CH 3 (PR 3 ) 2 [28]), an octahedral d 6 ML 5 fragment (RuCOCl(PR 3 ) 2 , SnCl 3 [29], Mn 2 (CO) 9 [30]), or a d 6 CpML 2 fragment (CpFe þ (CO) 2 [31,32]). Some exceptions occur for the d 6 ML 5 [Os(NH 3 ) 5 ] 2þ fragment, the coordination is h 2 [33,34] and, in the case of the d 6 CpRe þ NO(PR 3 ) fragment, the coordination is h 1 for ketones [35] and h 2 for aldehydes [36,37] as in the case of CpRe(CO) 2 [38].…”

Section: Introductionmentioning

confidence: 99%