Antimony–Carbon bond activation in a Pt(II) complex: The crystal structure of [Pt(9S3)(SbPh3)(Ph)](PF6)·CH3NO2

Grant, Gregory J.; Benefield, Desirée A.; VanDerveer, Donald G.

doi:10.1016/j.jorganchem.2009.11.010

Cited by 9 publications

(7 citation statements)

References 16 publications

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“…During crystallization of the previously discussed Sb thiacrown complex, [Pt( [9]aneS 3 )(SbPh 3 ) 2 ] 2+ , a second compound formed and was then structurally characterized as the mono(triphenylstibine)-phenyl complex [Pt( [9]aneS 3 )(SbPh 3 )(Ph)] + . 61 The product is formed via Sb-C bond activation in the triphenylstibine. The environment around the Pt(II) center consists of a [S 2 SbC + S 1 ] coordination sphere containing the [9]aneS 3 , a single SbPh 3 , and a σ-bonded anionic phenyl group.…”

Section: Other Pnictogen Ligands With [9]anesmentioning

confidence: 99%

Pnictogen–thiacrown complexes with Pt(ii) and Pd(ii)

Grant

2012

Dalton Trans.

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Platinum(II) and palladium(II) complexes of the trithiacrown [9]aneS(3) containing a range of Group 15 donors are reviewed. These complexes have the general formula [M([9]aneS(3))(L(2))](n+) where L represents at least one Group 15 donor. Complexes involving pnictogens, with the exception of bismuth, are observed. The complexes generally have an elongated square pyramidal geometry with a long distance interaction to the third sulphur of the [9]aneS(3) which forms the apex of the square pyramid. This axial metal-sulphur distance is quite sensitive to the donor properties of L. Poorer donors such as Sb and As ligands show short axial distances whereas the better N donor ligands show longer distances. Pt(II) complexes of the formula [Pt([9]aneS(3))(EPh(3))(2)](2+) (E = P, As, Sb) show a considerable distortion towards a trigonal bipyramidal geometry due to intramolecular π-π interactions. Over seventy of these types of complexes have been crystallographically characterized and are discussed in this article. Other unique features of the complexes, including NMR spectroscopy, redox chemistry, and electronic spectroscopy, are also discussed.

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Section: Other Pnictogen Ligands With [9]anesmentioning

confidence: 99%

Pnictogen–thiacrown complexes with Pt(ii) and Pd(ii)

Grant

2012

Dalton Trans.

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“…Details of the structure refinement are given in Table S1, SI. Selected bond distances (Å) and angles ( ): Pd1-S1 = 2.3253(4), Pd1-S2 = 2.3311(5), Pd1-Cl1 = 2.3005(4), Pd1-Cl2 = 2.3011(5); ∠Cl1-Pd1-S1 = 86.286 (16), ∠Cl2-Pd1-S2 = 84.683 (18), ∠S1-Pd1-S2 = 173.760( 16), ∠Cl1-Pd1-Cl2 = 179.347 (19) endocomplexes, an oxygen atom on the ligand is directed toward the inner side of the central metal. The oxygen atom of the endocomplex plays the role of a weak electron donor group to the central Pd (II) metal.…”

Section: Synthesis Of Cationic Palladium (Ii) Acetylacetonate Complexesmentioning

confidence: 99%

“…Ligand L4 assumes a facial coordination mode in 4b. Complex 4b has a distorted square planar geometry for palladium, shown by the ∠O3-Pd1-O2 and ∠S1-Pd1-S2 bond angles of 93.2(6) and 91.23 (18) , respectively. The average Pd-S bond distance of 2.275 Å is comparable with those found in other Pd (II) complexes of macrocyclic thioethers.…”

Section: X-ray Crystal Structure Of 4bmentioning

confidence: 99%

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Suslov

Abramov

Babenko

et al. 2021

Applied Organom Chemis

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The Pd (II) complexes trans-[PdCl 2 (μ-L)] 2 and [Pd(acac)(L)][BF 4 ] (L = RS (CH 2 ) 2 O(CH 2 ) 2 SR, R = Me, Et, n Pr, i Pr, n Bu, i Bu, n-hexyl, benzyl) were obtained through the reaction of Pd(cod)Cl 2 or [Pd(acac)(MeCN) 2 ][BF 4 ] with one equivalent of oxadithioether (L). The structural features of these complexes were analyzed by nuclear magnetic resonance (NMR) and Fouriertransform infrared spectroscopy (FTIR), as well as electrospray ionisation mass spectrometry and density functional theory calculations. The complexes diμ-(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 )-bis[trans-dichloropalladium (II)] and (acetylacetonate-κ 2 O,O 0 )(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S, S 0 )palladium (II) tetrafluoroborate were characterized by X-ray diffractometry. The X-ray structures of each complex indicate an axial M-O interaction formed by the endodentate conformation of the oxadithioether ligand. Palladium (II) dichloride complexes with oxadithioethers were demonstrated to have a 16-membered dinuclear structure with a trans-configured S 2 PdCl 2 fragment. In the case of cationic palladium acetylacetonate complexes, only mononuclear complexes with a cis configuration of the oxadithioether fragment were observed. Variable temperature 1 H and 13 C NMR studies of the complexes demonstrate dynamic bonding of the oxadithioether ligands consistent with the presence of diastereoisomers that differ in the orientation of the S-R groups along with both endodentate and exodentate bonding modes in solution. FTIR studies of the complexes indicate the presence of isomers in the solid state. The palladium catalyst precursors trans-[PdCl 2 (μ-L)] 2 and [Pd (acac)(L)][BF 4 ] were found to be active in the addition polymerization of norbornene. In the presence of cocatalysts, such as diisobutylaluminum chloride and boron trifluoride etherate, Pd (II) complexes exhibited activities in the range of 10 5 to 10 7 g of polymer (mol of Pd) À1 h À1 . The catalyst systems

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“…Also crystallisation of [Pt(9S3)(SbPh 3 ) 2 ] 2+ results in Sb-C bond cleavage and formation of [Pt(9S3)(SbPh 3 )(Ph)] + . 121 The reaction of [Re(Z 5 -C 5 H 5 ) 2 H] with bismuth alkoxides has allowed the preparation of a compound with rhenium-bismuth bonds [Re(Z 5 -C 5 H 5 ) 2 (BiR 2 )]. 122 ] which has a tetrahedral Bi 4 core with each face bridged by a Fe(CO) 3 group and an additional Fe(CO) 4 Z 1 -coordinated to each Bi.…”

Section: Arsenic Antimony and Bismuthmentioning

confidence: 99%