Synthesis and characterization of palladium(II) and platinum(II) complexes of Me3MCH2SeR (M = Si, Ge; R = Me, Ph) and crystal structures of trans-(Me3SiCH2SeMe)2PdCl2 and trans-(Me3GeCH2SeMe)2PtCl2

Chadha, Raj K.; Chehayber, Jaafar M.; Drake, John E.

doi:10.1021/ic00225a007

Cited by 20 publications

(6 citation statements)

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“…Only van der Waals interactions are found between the layers. In the case of trans ‐[MCl 2 {Te(CH 2 SiMe 3 ) 2 } 2 ] [M = Pt ( 2t ), Pd ( 3t )] the respective H ··· Cl hydrogen bonds of 2.765(2)–2.882(2) Å and 2.761(1)–2.827(1) Å result in the formation of skewed stacks like in trans ‐[MCl 2 {Se(Me)CH 2 QMe 3 ) 2 }],12 [MCl 2 (SeMeTh) 2 ] (M = Pd, Pt; Q = Si, Ge; Th = 2‐thienyl C 4 H 3 S),13 and [PdCl 2 (SeEt 2 ) 2 ] 17. By contrast to cis ‐[PdCl 2 (TeMeR) 2 ] (R = thienyl, furyl C 4 H 3 O),13 trans ‐[PtI 2 (TeMePh) 2 ]),14 cis ‐[PdCl 2 { meso ‐(TeC 6 H 4 OMe‐4) 2 CH 2 }],30 and cis ‐[PdBr 2 { meso ‐(PhTe) 2 (CH 2 ) 3 }],31 no Te ··· Cl interactions were found in 2c or in 2t and 3t .…”

Section: Resultsmentioning

confidence: 99%

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

2007

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The mononuclear (telluroether)platinum and -palladium complexes cis- [ ] (3t) have been prepared from bis(trimethylsilylmethyl)tellane and bis(benzonitrile)dichloridoplatinum and -palladium and structurally characterized by single-crystal X-ray diffraction and NMR spectroscopy. The isomer distribution of the platinum complex depends on the initial molar ratio of the reactants. When [PtCl 2 (NCPh) 2 ] was used in excess, 2c was the main product. Upon increasing the initial ligand/metal molar ratio, the relative amount of 2t increased. The stoichiometric reaction afforded approximately equal amounts of the cis and trans isomers. Further increase of the initial amount of the ligand yielded 2t. The mononuclear palladium complex was

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Section: Resultsmentioning

confidence: 99%

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

2007

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“…The Pd−Se bond distances (see Tables and ) are comparable with previous values ( cf. Pd−Se, 2.429(1) and 2.424(7) Å in Pd(II) complexes of dialkylseleno ethers and 2.428(1) and 2.435(2) Å in [Pd(16Se4)][PF 6 ] 2 ·2MeCN 5 ). The relatively high precision in the structure of 2 clearly reveals a small but significant asymmetry in the Pd−Se bond lengths to trans -related selenium atoms.…”

Section: Resultsmentioning

confidence: 99%

Stereochemical Analysis of Palladium(II) Complexes of the Selenium Coronands 1,5,9,13-Tetraselenacyclohexadecane and 1,5,9,13,17,21-Hexaselenacyclotetracosane

Batchelor

Einstein

et al. 1996

Inorg. Chem.

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Crystal structures for [Pd(16Se4)][BF 4 ] 2 (1) (16Se4 ) 1,5,9,13-tetraselenacyclohexadecane) and [Pd(16Se4)]- [BF 4 ]Cl (2) both contain the [Pd(16Se4)] 2+ ion which has square-planar coordination about Pd and a stereochemistry (denoted c,c,c) in which all of the selenium nonbonding valence electron pairs are mutually cis with respect to the coordination plane. In both structures the conformation adopted by the cation deviates slightly but significantly from molecular mm (C 2V ) symmetry. The asymmetry is most clearly resolved for 2, in which the Pd-Se bond lengths vary significantly (2.444(1)-2.463(1) Å). For 1: T ) 295 K; fw ) 764.2; space group Pnma; Z ) 4; a ) 12.356(1) Å; b ) 10.397(1) Å; c ) 16.233(2) Å; V ) 2193.7 Å 3 ; R F ) 0.036 for 997 data (I o g 2.5σ(I o )) and 131 variables. For 2: T ) 295 K; fw ) 712.8; space group P1 h; Z ) 2; a ) 7.2377(4) Å; b ) 10.7784(7) Å; c ) 12.9523(9) Å; R ) 76.607(6)°; β ) 86.020(6)°; γ ) 85.186(5)°; V ) 978.17 Å 3 ; R F ) 0.023 for 2134 data (I o g 2.5σ(I o )) and 214 variables. The 77 Se, 1 H, 13 C, and 1 H-13 C correlated NMR spectra for 1 in D 2 O solution were fully assigned. At room temperature, [Pd(16Se4)] 2+ occurs in D 2 O solution predominantly as the c,t,c and c,c,c stereoisomers. Variable temperature NMR spectroscopic results demonstrate that at an elevated temperature (389 K) configurational interconversion is rapid on the 1 H-NMR time scale. Cyclic voltammetry of 1 and 2, in MeCN solution with Pt electrodes, shows that the redox reaction of the pair Pd(II)/Pd(I) is irreversible with cathodic peak potentials at -0.56 and -0.47 V vs SCE, respectively. The crystal structure of [(PdCl) 2 (24Se6)]-[BF 4 ] 2 ‚2CH 2 Cl 2 (3‚2CH 2 Cl 2 ) reveals a complex dication in which two individual palladium(II) centers are each bound by three adjacent selenium atoms. Both palladium centers display square planar coordination with a chlorine atom occupying the fourth site. The complex exhibits trans relationships between adjacent pyramidal selenium centers and adopts a conformation which has only approximate m (C s ) symmetry. The mutually trans Pd-Se bond lengths range from 2.421(1) to 2.428(1) Å. The Pd-Se bond lengths trans to the chlorine atom are 2.372-(1) and 2.364(1) Å, and the corresponding Pd-Cl bond lengths are 2.343(2) and 2.351(3) Å. For 3‚2CH 2 Cl 2 : T ) 195 K; monoclinic, space group P2 1 /c; Z ) 4; a ) 16.421(2) Å; b ) 19.353(2) Å; c ) 12.397(3) Å; β ) 91.16(2)°; V ) 3938.9 Å 2 ; R F ) 0.037 for 3793 data (I o g 2.5σ(I o )) and 409 variables. Cyclic voltammetry of 3 in MeCN solution with Pt electrodes shows an irreversible cathodic peak potential at -0.58 V vs SCE corresponding to a Pd(II)/Pd(I) pair. Electrolysis in MeCN confirms that this is a two-electron reduction for the complex.

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“…The C(1)-Se-Hg angle is indeed slightly larger in 1 and 2 (100.8(9) and 100.5(6)" respectively) than in 3 (98.3(6)"). All are considerably smaller than the equivalent C-Pd-Se bond in (Me3SiCH2SeMe)2-PdC12, which is 108.0(2)" (8). In the latter compound the Pd-Se bond is relatively short, suggesting that PdC12 is a better Lewis acid than HgC12.…”

Section: Resultsmentioning

confidence: 90%

“…However, there are few examples of crystallographic studies of such complexes. Apart from our recent description of the structures of trans-(Me3SiCH2SeMe)2PdC12 and tran~-(Me~SiCH~SeMe)~PtCl~ (8), there are three other reports of selenoether-metal complexes; trans-(Et2Se)2PdC12 (9), (MeSeCHCH3)2PdC12 ( l o ) , and tr~ns-(O(CH~)~Se)2PtBr2 (11).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of Hg(II) complexes of Me₃MCH₂SeMe, (M = Si, Ge). Crystal structures of [HgX₂(Me₃SiCH₂SeMe)]₂, X = Cl, Br, I

Chadha¹,

Drake²,

McManus³

et al. 1987

Can. J. Chem.

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. Can. J. Chem. 65, 2305 (1987). Complexes of the general formula [HgX2(Me3MCH2SeMe)I2, where M = Si, Ge; X = C1, Br, I, have been prepared and characterized by 'H nuclear magnetic resonance and Raman spectroscopy. Crystal structures of [HgX2(Me3SiCH2SeMe)12, where X = C1, Br, and I (1, 2, and 3 respectively), show that they have centrosymmetric dinuclear structures. The crystals of 1 and 2 are monoclinic, while those of 3 are triclinic. For 1: P2'/c, a = 14.235(1 l), b = 6.551(6), c = 14.21 l(9) A, P = 117.33 (5) [Traduit par la revue]

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Synthesis and characterization of palladium(II) and platinum(II) complexes of Me3MCH2SeR (M = Si, Ge; R = Me, Ph) and crystal structures of trans-(Me3SiCH2SeMe)2PdCl2 and trans-(Me3GeCH2SeMe)2PtCl2

Cited by 20 publications

References 7 publications

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

Stereochemical Analysis of Palladium(II) Complexes of the Selenium Coronands 1,5,9,13-Tetraselenacyclohexadecane and 1,5,9,13,17,21-Hexaselenacyclotetracosane

Synthesis and characterization of Hg(II) complexes of Me₃MCH₂SeMe, (M = Si, Ge). Crystal structures of [HgX₂(Me₃SiCH₂SeMe)]₂, X = Cl, Br, I

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Synthesis and characterization of palladium(II) and platinum(II) complexes of Me3MCH2SeR (M = Si, Ge; R = Me, Ph) and crystal structures of trans-(Me3SiCH2SeMe)2PdCl2 and trans-(Me3GeCH2SeMe)2PtCl2

Cited by 20 publications

References 7 publications

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

Formation and Characterization of Platinum and Palladium Complexes of Bis(trimethylsilylmethyl)tellane

Stereochemical Analysis of Palladium(II) Complexes of the Selenium Coronands 1,5,9,13-Tetraselenacyclohexadecane and 1,5,9,13,17,21-Hexaselenacyclotetracosane

Synthesis and characterization of Hg(II) complexes of Me3MCH2SeMe, (M = Si, Ge). Crystal structures of [HgX2(Me3SiCH2SeMe)]2, X = Cl, Br, I

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Synthesis and characterization of Hg(II) complexes of Me₃MCH₂SeMe, (M = Si, Ge). Crystal structures of [HgX₂(Me₃SiCH₂SeMe)]₂, X = Cl, Br, I