Cationic rhodium(I) complexes.  4.  Oxidative addition reactions of di(tertiary phosphine and arsine) complexes

Mague, Joel T.; Davis, Edward J.

doi:10.1021/ic50167a028

Cited by 19 publications

(4 citation statements)

References 26 publications

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“…Selected bond lengths and angles are listed in Table 3. The Rh᎐S(1) bond length 12 The Rh᎐S(2) bond length of 2.404(5) Å is 0.055 Å longer than Rh᎐S(1), probably due to the stronger trans influence of the PPh 2 relative to the NH 2 group. The Rh᎐P(1) bond length [2.295(4) Å] is similar to those in complexes 2 (average 2.309 Å) and 8ؒClؒ2EtOH (average 2.300 Å).…”

Section: Oxidative Addition Of Cyclo-octasulfurmentioning

confidence: 96%

“…presumably via an intermediate containing a Cl᎐Rh᎐CH 2 Cl moiety. In the case of oxidative addition of cyclo-octasulfur, the rhodium() complexes containing dmpe, dppe, 10 PhP[(CH 2 ) 3 PPh 2 ] 2 11 and cis-Ph 2 AsCH᎐ ᎐ CHAsPh 2 12 produced the corresponding η 2 -S 2 complexes of rhodium(), whereas [Rh(η 13 There have been no published reports of oxidative addition of cyclo-octasulfur to complexes containing P᎐N hybrid ligands. For the oxidative addition of dioxygen, a few examples have been established for rhodium() complexes having such ligands, in particular 15 Here, we describe the structures of the oxidative-addition products, trans(Cl,C)cis-…”

mentioning

confidence: 99%

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Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine

Kashiwabara¹,

Morikawa²,

Suzuki³

et al. 1997

J. Chem. Soc., Dalton Trans.

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Section: Oxidative Addition Of Cyclo-octasulfurmentioning

confidence: 96%

mentioning

confidence: 99%

Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine

Kashiwabara¹,

Morikawa²,

Suzuki³

et al. 1997

J. Chem. Soc., Dalton Trans.

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“…This band at 540 cm −1 falls in the range expected for SS stretching vibrations (ν SS ) of (η 2 -persulfido)iridium(III) complexes. 110,111 Unfortunately, the shifted band for 6a-34 S 2 (expected, 524 cm −1 ) is masked by other signals in the spectrum and could not be observed. The band at 540 cm −1 is also absent from the IR spectra of 1a and the decay The reaction of 6a with 10 equiv of PPh 3 yielded ca.…”

Section: Figure 27mentioning

confidence: 96%

Guanidinato and amidinato complexes of iridium(I)

Kelley¹

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“…215,216 Many aspects of the oxidation of Wilkinson's complex, [RhCl(PPh 3 ) 3 ], to form a distorted octahedral complex with a side-on η 2 -O 2 ligand have been reported, including the synthesis, 217,218 degradation 219 and use as an oxidation catalyst. 220,221 Numerous other rhodium dioxygen complexes have been reported with monophosphine [222][223][224][225][226][227][228][229][230][231] and diphosphine [232][233][234][235][236][237][238][239] ligands.…”

Section: Dioxygen and Oxo Complexesmentioning

confidence: 99%

Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

Nelson¹

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<p>This thesis provides an account of research into a group of diphosphine ligands with a rigid xanthene backbone and tert -butyl substituents on the phosphorus atoms. The three ligands have different groups in the bridgehead position of the backbone (CMe₂, SiMe₂, or S) which change the natural (calculated) bite-angle of the ligand. The coordination chemistry of these t -Bu-xantphos ligands with late-transition metals has been investigated with a focus on metal complexes that may form in catalytic reactions. The three t -Bu-xantphos ligands were synthesised by lithiation of the backbone using sec -butyllithium/TMEDA and treatment with PtBu₂Cl. The natural biteangles of the Ph-xantphos (111.89–114.18°) and t -Bu-xantphos (126.80–127.56°) ligands were calculated using DFT. The bite-angle of the t -Bu-xantphos ligands is larger due to the increased steric bulk of the tert -butyl substituents. The electronic properties of the t -Bu-xantphos ligandswere also investigated by synthesis of their phosphine selenides. The values of ¹J PSe (689.1–698.5Hz) indicate that the t -Bu-xantphos ligands have a higher basicity than Ph-xantphos between PPh₂Me and PMe₃. The silver complexes, [Ag(t -Bu-xantphos)Cl] and [Ag(t -Bu-xantphos)]BF₄ were synthesised with the t -Bu-xantphos ligands. In contrast to systems with phenyl phosphines, all species were monomeric. [Rh(t -Bu-xantphos)Cl] complexes were synthesised, which reacted with H₂, forming [Rh(t -Bu-xantphos-ĸP,O,P ’)Cl(H)₂] complexes, and with CO, forming [Rh(t -Bu-xantphos)(CO)₂Cl] complexes. The [Rh(t -Bu-xantphos)Cl] species are air-sensitive readily forming [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)] complexes. The crystal structure of [Rh(t -Bu-xantphos)Cl(ƞ²-O₂)], contained 15% of the dioxygen sites replaced with an oxo ligand. This is the first crystallographic evidence of a rhodium(III) oxo complex, and only the third rhodium oxo species reported. The coordination chemistry of the ligands with platinum(0) and palladium(0) showed some differences. [Pt(t -Bu-xantphos)(C₂H₄)] complexes were synthesised for all three ligands. However, reaction with [Pt(nb)₃] produced a mixture of [Pt(t -Bu-xantphos)] and [Pt(t -Bu-xantphos)(nb)] for t -Bu-sixantphos and t -Buthixantphos. Although few examples of isolable [Pt(PP)] complexes with diphosphines have been reported [Pt(t -Bu-thixantphos)] was isolated by removal of the norbornene. t -Bu-Xantphos formed small amounts of [Pt(t -Bu-xantphos)] initially, which progressed to [Pt(t -Bu-xantphos)H]X. The analogous reactions with [Pd(nb)₃] gave [Pd(t -Bu-xantphos)] and [Pd(t -Bu-xantphos)(nb)] complexes in all cases. [Pt(t -Bu-thixantphos)(C₂H₄)] and [M(t -Bu-thixantphos)] (M = Pd, Pt) react with oxygen forming [Pt(t -Bu-thixantphos)(ƞ²-O₂)], which reacts with CO to give [Pt(t -Bu-thixantphos-H-ĸ-C,P,P ’)OH] through a series of intermediates. [M(t -Bu-xantphos)Cl₂] (M = Pd, Pt) complexes were synthesised, showing exclusive trans coordination of the diphosphine ligands. The X-ray crystal structure of [Pt(t -Bu-thixantphos)Cl₂] has a bite-angle of 151.722(15)°. This is the first [PtCl₂(PP)] complex with a bite-angle between 114 and 171°. In polar solvents a chloride ligand dissociates from the [Pt(t -Bu-xantphos)Cl₂] complexes producing [Pt(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺. The analogous [Pd(t -Bu-xantphos-ĸP,O,P ’)Cl]⁺ complexes were formed by reaction of the dichlorides complexes with NH₄PF₆. The [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ pincer complexes were the only product from reaction with [Pt(C₆H₁₀)ClMe], with the stronger trans influence of the methyl ligand promoting loss of the chloride. The formation of the pincer complexes was further explored using DFT. The values of J PtC for the methyl carbons in the [Pt(t -Bu-xantphos-ĸP,O,P ’)Me]⁺ complexes, and J RhH for the hydride trans to the oxygen atom in the [Rh(t -Buxantphos-ĸP,O,P ’)Cl(H)₂] complexes were largest for t -Bu-sixantphos, then t -Buthixantphos, then t -Bu-xantphos. The trans influence of the t -Bu-xantphos oxygen donor follows the trend t -Bu-sixantphos < t -Bu-thixantphos < t -Bu-xantphos.</p>

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Cationic rhodium(I) complexes. 4. Oxidative addition reactions of di(tertiary phosphine and arsine) complexes

Cited by 19 publications

References 26 publications

Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine

Oxidative additions of dichloromethane and cyclo-octasulfur to rhodium(I) complexes containing (2-aminoethyl)-dimethylphosphine or -diphenylphosphine

Guanidinato and amidinato complexes of iridium(I)

Synthesis, Properties, and Coordination Chemistry of t-Bu-Xantphos Ligands

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