Crystal and molecular structure of trans-(methyl)chlorobis(triphenylphosphine)platinum(II)

doi:10.1016/S0020-1693(00)89337-8

Inorganica Chimica Acta

Volume 47, 1981, Pages 249-254

https://doi.org/10.1016/S0020-1693(00)89337-8 Get rights and content

Abstract

The crystal and molecular structure of trans-Pt(CH₃)Cl(PPh₃)₂ has been determined. Crystals are monoclinic, space group P2₁/n, a = 11.813(7), b = 23.523(9), c = 12.306(7) Å, β = 111.7(1)°, Z = 4.2676 observed reflections were measured with a diffractometer; the structure was solved by Patterson-Fourier methods and refined by full-matrix least-squares to a final conventional R of 0.049 (Rw = 0.041). The crystal contains discrete neutral trans-Pt(CH₃)Cl(PPh₃)₂ molecules, separated by normal van der Waals contacts. The complex is a typical square-planar Pt(II) species. Structural parameters: PtCl = 2.431(3), PtC = 2.08(1) PtP = 2.295(3) and 2.298(3) Å; P(1)PtCl = 88.1(1), P(1)PtC(1) = 92.3(4), P(2)PtCl = 88.1(1) and P(2)PtC(1) = 91.6(4)°.

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Organophosphines in organoplatinum complexes - Structural aspects of trans-PtP<inf>2</inf>CCl derivatives
2016, Journal of Organometallic Chemistry
Citation Excerpt :
Such complexes are: [Pt(PMe3)2{CC(Ph)B(Cl) = N(SiMe3)2}(Cl)] [6], [Pt(PMe3)2(C9H7O2)(Cl)] [7]; [Pt(PEt3)2(C9H4N3O)(Cl)] [7], [Pt(PEt3)2(CO)(Cl)](SiF6) [8], [Pt(PEt3)2(o-tolyl)(Cl)] [9], [Pt(PEt3)2{C(Cl) = PC6H2But3-2,4,6}(Cl)] [10], [Pt(PEt3)2{C{P(H) = O} = C6H2But3-2,4,6}(Cl)] [10], [Pt(PEt3)2(C6H4Ph-2)(Cl)] [11], [Pt(PEt3)2{C{P(Cl)} = C6H2But3-2,4,6}(Cl)] [12], [Pt(PEt3)2{CN(ptolyl)}(Cl)] [13], [Pt(PEt3)2(C6Cl5)(Cl)] [14], [Pt(PEt3)2(C36H23N2)(Cl)] [15]; [Pt(PBu3)2{CC(Pr) = C(Pr)C(Pr) = C(Pr)O}(Cl)]PF6 [16]; [Pt(PPh3)2(CO)(Cl)](BF3Cl) [17], [Pt(PPh3)2(Me)(Cl)] [18], [Pt(PPh3)2(CH2Cl)(Cl)] [19], [Pt(PPh3)2(CF3)(Cl)] [20], [Pt(PPh3)2(C6F5)(Cl)] [21], [Pt(PPh3)2(Ph)(Cl)] (at 295 K) [22], (at 173 K) [23], [Pt(PPh3)2(C6H4OMe-4)(Cl)] [24], [Pt(PPh3)2(CH2CN)(Cl)] [25], [Pt(PPh3)2(CO2Me)(Cl)] [26], [Pt(PPh3)2(COMe)(Cl)]CHCl3 [27], [Pt(PPh3)2(CCCl)(Cl)] [28], [Pt(PPh3)2(allyl)(Cl)] (2 isomers) [29,30], [Pt(PPh3)2{CCC(Me)2}(Cl)]2C6H6 [31], [Pt(PPh3)2{CCC(Me)2}(Cl)]2/3CHCl3 (two independent molecules) [32], [Pt(PPh3)2(CH2COMe)(Cl)]CHCl3 [33], [Pt(PPh3)2{CH2CC(Me) = CH2}(Cl)]C6H6 [34], [Pt(PPh3)2(CH=CHPh)(Cl)]CH2Cl2 (monoclinic) [35], (triclinic) [36], [Pt(PPh3)2{CCC(OH)Me2}(Cl)].0.5toluene [37], [Pt(PPh3)2{CC(OH)(Me)(Et)}(Cl)]Me2CO [37], [Pt(PPh3)2(COCOPh)(Cl)] [38], [Pt(PPh3)2((COPr)(Cl)] [39], [Pt(PPh3)2(COC6H13)(Cl)] [40], [Pt(PPh3)2. ( COCH2CH2Ph)(Cl)]EtOH [41], [Pt(PPh3)2{CHC(CMe)C(O)CC(CMe3)}(Cl)]0·5CH2Cl2.
In this review are classified and analyzed structural parameters of over one hundred and thirty monomeric organoplatinum complexes with trans- PtP₂CCl inner coordination sphere. These complexes crystallized in four crystal systems: tetragonal (×2), orthorhombic (×22), triclinic (×41) and monoclinic (×69). These complexes from the coordination mode of the respective donor ligands, which build up inner coordination sphere, trans- PtP₂CCl, can be divided into the five groups. There is variety of donor ligands, monodentate PL,CL and Cl; homobidentate- P,P’; heterobidentate- P/C and P/Cl, and even heterotridentate- P,C,P donor ligands. The chelating ligands created variety of metallocyclic rings. There are several examples which exist in two isomeric forms and some other examples which contain two crystallographically independent molecules within the same crystal. These isomeric forms as well as independent molecules are example of distortion isomerism. The comprehensive mean Pt-L bond distances elongated in the order: 2.01 Å (C, trans to Cl) < 2.287 Å (P, trans to P) < 2.390 Å (Cl, trans to C).
Synthesis and characterization of Pt(II) and Pd(II) PTA and DAPTA complexes
2014, Polyhedron
A series of four-coordinate air stable and water soluble cis- and trans-Pt(II) and Pd(II) complexes containing two PTA or DAPTA ligands (PTA = 1,3,5-triaza-7-phosphaadamantane; DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) with the general formulas, [PtR₂(PTA)₂], [M(Me)X(PTA)₂], [Pt(Et)X(PTA)₂], [MR₂(DAPTA)₂], [MX₂(DAPTA)₂], and [M(Me)X(DAPTA)₂] (where M = Pt or Pd; R = Me, Et, CCR (R = Ph, SiMe₃); X = Cl, Br, I) were prepared by ligand displacement starting from [M(R)₂(COD)], [M(R)(X)(COD)] or precursors or metathesis reactions utilizing [MCl₂(PR₃)₂] precursors in good yields (63%–90%). The complexes were characterized by multinuclear NMR, IR, MS, and elemental analysis experiments and in some cases by X-ray crystallography studies. Complexes, cis-[PtMe₂(PTA)₂] (cis-1), trans-[Pt(Me)Cl(PTA)₂] (trans-3a), trans-[PtCl₂(PTA)₂] (trans-4), trans-[Pt(CCPh)₂(PTA)₂] (trans-6), and trans-[PtI₂(DAPTA)₂] (trans-13c) were characterized by X-ray crystallography. The molecular structures reveal, in general, distorted square planar geometries at the metal center. For the DAPTA complexes, both syn- and anti-conformations of the DAPTA rings were observed depending upon the nature of the groups at the metal center.
Trans influence in platinum(II) complexes. Phenylation of Pt(II) dialkylsulfide complexes by BPh<sup>-</sup><inf>4</inf> and SnPh<inf>3</inf>H. Crystal structures of two polymorphs of trans-chlorobis(dimethylsulfide)(phenyl)platinum(II)
1996, Journal of Organometallic Chemistry
Two methods of phenylation of platinum(II) complexes are described, one by heating [PtCl(dms)₃](BPh₄) and another starting from triphenyltin hydride and [PtCl₂(dms)₂], dms = dimethylsulfide. Two different polymorphs of trans-[PtPhCl(dms)₂] are obtained, one monoclinic and one triclinic. The monoclinic form contains two crystallographically different complexes. The main difference between the molecular geometries in the polymorphs is the orientation of the dms ligands. Distances found are PtCl, 2.403–2.420; PtS, 2.279–2.298 and PtC, 1.99–2.00 Å. A comparison of some PtCl bond distances obtained from the literature reveals that the trans influence increases in the following order: $Cl < S ⪕ Sn, P < C, H < Si$ .
The Bonding of Metal-Alkynyl Complexes
1995, Advances in Organometallic Chemistry
The chemistry of metal–alkynyl compounds is developing at a rapid pace. The bonds of alkynyl ligands, like those of organic alkynes have been shown to participate in a rich set of chemical transformations. Electronic-absorption band maxima and extinction coefficients have been reported for a large number of metal–alkynyl complexes. Casual comparisons of electronic-absorption band energies or intensities among a series of compounds in the absence of such experiments are not without the risk of misinterpretation because a variety of important effects not associated with the presence or absence of M-CCR π-bonding may be operative such as mixings between electronic states of identical symmetry but different orbital character. The best and simplest means of placing the M–C bond distances of metal–alkyl complexes in a context that allows insight into whether or not they manifest M-CCR π-interactions is to compare them to M–C bond distances of complexes where such effects are expected to be insignificant, as for metal–alkynyl compounds.
Synthesis and characterization of sterically encumbered Li, Na, and K aryl tellurolates, and some Pt(II), Ir(I), and Cd(II) derivatives
1993, Journal of Organometallic Chemistry
The synthesis, isolation, and characterization of several alkali metal aryl tellurolates of general formula (2,4,6-R₃C₆H₂)TeM(sol) _n (R  Me, ⁱPr, ^tBu; M  Li, Na, K; sol = THF, n = 1.33, 1.5, 2.5, 3; sol = DME, n = 1; sol = TMEDA, n = 1; sol = 18-crown-6, n = 1) is reported. Reduction of (2,4,6-Me₃C₆H₂)₂Te₂ and (2,4,6-ⁱPr₃C₆H₂)₂Te ₂ with 2 equiv of LiEt₃BH in THF affords the corresponding lithium tellurolates 1 and 2. Direct Te insertion into the CLi bond of (2,4,6-^tBu₃C₆H₂)Li(THF)₃ in THF produces 3, while a similar reaction of Te metal with (o-C₆H₄CH₂ NMe₂)Li affords the chelating tellurolate, 4. The action of Na/Hg amalgam on THF solutions of (2,4,6-Me₃C₆H₂)₂Te₂ or (2,4,6-ⁱPr₃C₆H₂)₂Te₂ followed by work-up with TMEDA or DME leads to the sodium tellurolates 5 and 6 respectively. Treatment of THF solutions of (2,4,6-ⁱPr₃C₆H₂)₂Te₂ with 2 equiv. of K^sBu₃BH gives the polymeric tellurolate, (2,4,6-ⁱPr₃C₆H₂)₂TeK(THF)_1.33, (7). The infinite ladder-like structure is broken by reaction with 18-crown-6, which affords the monomeric derivative, 8. Reaction of 2 or 3 with THF suspensions of cis-(PPh₃)₂PtCl₂ produces the air-stable cis-platinum tellurolates, 9 and 10, respectively. Reaction of 3 with trans-(PPh₃)₂Ir(CO)Cl, leads to the isolation of 11, a rare example of a Vaska's type complex with a cis-geometry, and only the second such structurally characterized derivative. Reaction of 4 with 1/2 equiv. of CdBr₂ produces 12, Cd[Te(o-C₆H₄CH₂NMe₂)]₂. Compounds 3, 4, 7, 10, and 11 have been characterized by single crystal X-ray diffraction.
Synthesis, chemical and electrochemical deprotonation reactions of aminocarbene complexes of palladium(II) and platinum(II). X-ray structure of {(PPh<inf>3</inf>)ClPt[μtsqb:COCH<inf>2</inf>CH<inf>2</inf>NC,N]} <inf>2</inf>
1991, Inorganica Chimica Acta
The diaminocarbene complexes cis-Cl₂(PPh₃)Pt[ $CN(Bu^{t})CH_{2} CH_{2} N$ H] (1) and cis-Cl₂Pt[ $CN(C_{6} H_{4} -p-OMe)CH_{2} CH_{2} N$ H]₂ (2) have been prepared by reaction of the corresponding isocyanide derivatives with aziridine/ClCH₂CH₂NH₃⁺Cl⁻ and aziridine alone, respectively. The aminooxycarbene complex cis-Cl₂Pt[ $CN(C_{6} H_{4} -p-OMe)CH_{2} CH_{2} O$ ]₂ (3) has been prepared by reaction of the bis-isocyanide derivative with 2-chloroethanol/n-BuLi. The dimeric complexes {(PPh₃)BrPd[μ- $CN(Me)CH_{2} CH_{2} N$ C,N]}₂ (4), {(PPh₃)ClPd[μ- $CN$ (C₆H₄-p-OMe)CH₂CH₂NC,N]}₂ (5), {(PPh₃)ClPt[μ- $CN(C_{6} H_{4} -p-OMe)CH_{2} CH_{2} N$ C,N]}₂ (6) have been prepared by deprotonation reaction of the NH group of the corresponding mononuclear derivatives with n-BuLi. The X-ray structure of {(PPh₃)ClPt[μ- $COCH_{2} CH_{2} N$ C,N]}₂ (7) is reported. The structural model was refined to R=0.055 (R_w=0.061) for 7442 independent reflections. Crystal data: triclinic, space group $P$ , a=19.564(3), b=16.497(3), c=13.243(2) Å, α=88.93(3), β=97.88(3), γ=91.97(3)° Z=4. The crystal contains two crystallographically independent dimer units and a disordered dichloroethane molecule. Each dimer is formed by two bridging carbene ligands which are coordinated to one platinum on one side via a PtN bond and to the second platinum via a PtC bond. The coordination geometry around each platinum atom is an irregular square with deviations in the tetrahedral direction of the bonded atoms. The anodic behaviour of these and related monocarbene, dicarbene or dinuclear dicarbene complexes has been studied by cyclic voltammetry and controlled potential electrolysis in aprotic media and shown to present irreversible oxidation waves commonly with a multi-electron character (up to four electrons) and involving liberation of protons (in a number similar to that of the transfered electrons) conceivably resulting from anodically induced NH or CH bond cleavage, the former at an amino group and the latter occurring at methylene groups activated by adjacent amino- or oxy-carbene moieties.

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Crystal and molecular structure of trans-(methyl)chlorobis(triphenylphosphine)platinum(II)

Abstract

Inorg. Chim. Acta

Adv. Organometal. Chem.

Inorg. Chim. Acta

J. Organometal. Chem.

J. Organometal. Chem.

Inorg. Chim. Acta

Inorg. Chim. Acta

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

Cryst. Struct Comm.

Trans. Met. Chem.

Cryst. Struct. Comm.

Sixth European Crystallographic Meeting

Sixth European Crystallographic Meeting

Chem. Rev.

J. Organometal. Chem.

Inorg. Chem.