The molecular and crystal structure of trans-hydridobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)platinum(II) [PtH(PPh3)2(p-CH3C6H4NNNC6H4CH3-p)]

doi:10.1016/S0022-328X(00)93216-9

Journal of Organometallic Chemistry

Volume 118, Issue 3, 12 October 1976, Pages 355-362

https://doi.org/10.1016/S0022-328X(00)93216-9 Get rights and content

Abstract

The structure of the title compound has been determined at room temperature from three-dimensional X-ray data collected by counter methods. The material crystallizes in the triclinic space group P $1$ with two molecules in a cell of dimensions a 14.649(2), b 15.082(2), c 10.929(1) Å, α 110.99(5)°, β 102.40(5)°, γ 84.54(5)°. Full-matrix least-squares treatment of 4673 observed intensities gave an unweighted R value of 0.069. The platinum atom has square-planar coordination with PtP(1) 2.268(5), PtP(2) 2.267(5), PtN(1) 2.09(2) Å. The presence of the hydrogen atom is inferred from IR and ¹H NMR data. The triazenido ligand, σ bonded to the metal through N(1), lies perpendicular to the coordination plane.

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Cited by (22)

Design, synthesis and reactivity with dichloro-bis(triphenylphosphine) platinum(II) of two triazenide compounds
2011, Inorganica Chimica Acta
Citation Excerpt :
The important feature of the structure is the monodentate bonding of the L− ligand to the Pt. The Pt–N bond length 2.078(5) Å is in agreement the value of 2.09(2) reported for trans-[PtH(dtt)-(PPh3)2] (dtt = 1,3-di-p-tolyltriazenido) [21] and is slightly shorter than the distance found in [NBu4][Pt(C6F5)2(PhNNNPh)(Cl)2] (2.1215 Å) [22]. The bond distance of Pt and Cl (2.3569(16) Å) is slightly longer than that found in [NBu4][Pt(C6F5)2(PhNNNPh)(Cl)2] [22].
In the presence of sodium nitrite, the reaction of methyl anthranilate and 2-aminopyridine or o-aminobenzoic acid gives two triazenes, 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) and 1-[(2-carboxymethyl)benzene]-3-[o-aminobenzoic acid]triazene (H₂L′), respectively. In the presence of Et₃N, the reaction of Pt(PPh₃)₂Cl₂ and HL or H₂L′ produces two triazenido platinum(II) complexes, Pt(PPh₃)₂(L)Cl (1) and Pt(PPh₃)₂(L′) (2), respectively, which have been characterized by X-ray crystallography, ³¹P NMR spectra, UV–Vis spectra, emission spectra and cyclic voltammetry. When excited at 310 nm, complexes 1 and 2 show luminescence at 432 and 442 nm, respectively, which is consistent with the trend of the lowest-energy absorption wavelengths of 1 (376 nm) and 2 (379 nm). Complexes 1 and 2 exhibit one or two redox waves and follow the order 1 (0.97 V) → 2 (0.89 and 0.07 V), which is also in accordance with the trend of the lowest-energy absorption spectra of 1 (376 nm) and 2 (379 nm).
CpCr(CO)<inf>3</inf><sup>■</sup>-initiated N-N bond cleavage in a thiotetrazole ligand in a cyclopentadienylchromium complex
2005, Journal of Organometallic Chemistry
The tetrazolylthiolato complex CpCr(CO)₃(STz) (4a) was obtained from the facile reaction between [CpCr(CO)₃]₂ (Cp = C₅H₅) (1) and 5,5′-dithiobis(1-phenyl-1H-tetrazole), (abbrev. (PhN₄CS)₂ or (STz)₂). Further reaction of 4a with 1 under thermolytic conditions led to isolation of low yields of the cubane-like complexes Cp₄Cr₄S₃(μ₃-N₃Ph) (5), Cp₄Cr₄S₂(μ₃-CO)(μ₃-NCCrCp(CO)₂) (6), Cp₄Cr₄S₂(μ₃-N₃Ph)(μ₃-NCCrCp(CO)₂) (7) and Cp₄Cr₄SO₂(μ₃-NPh) (8), containing μ₃-phenyltriazenido, imidocarbyne and phenylimido groups at the corners of cuboids, in addition to μ₃-sulfide, oxo or carbonyl groups. The predominant products were the decarbonylation derivative of 1, i.e. [CpCr(CO)₂]₂(CrCr) (9), together with [CpCr(CO)₂]₂S (10) and its thermolytic cuboidal derivatives, mainly Cp₄Cr₄S₂O₂ (11) and Cp₄Cr₄S₄ (13). 1-initiated homolytic fragmentation of the tetrazole ring was proposed to rationalize the formation of the derived cubanes. The structures of the complexes 4a, 6–8 and 11 have been determined by single X-ray diffraction analysis.
X-ray structure and fluxional behaviour of N,N′-di-p-fluorophenyltriazenido complex of nickel(II)
2000, Journal of Organometallic Chemistry
The Ni(II) triazenide complex, trans-(o-Tol)Ni(PEt₃)₂N₃Ar₂ (Ar=p-FC₆H₄) (1), was synthesized by the reaction of trans-(o-Tol)Ni(PEt₃)₂Br with Ar₂N₃Na. The crystal structure as well as the ¹H-, ¹⁹F- and ³¹P-NMR spectra in toluene-d₈ at different temperatures are reported. It was found that the triazenido group acts as a monodentate ligand. Complex 1 in solid state has a S-cis-structure with NiN(3) σ-bond and exists as a 3:1 mixture of two isomers with cisoid or transoid orientation of the Me group of the o-tolyl ligand relative to the N(1)N(2) bond. It was established that the N,N′-migration of (o-Tol)Ni(PEt₃)₂ group occurs in a solution of 1. The migration rate increases with the temperature increase in the range from −104 to −45°C. However, a further increase in the temperature slows down the process.
Synthesis, structure, and characterization of lanthanide complexes bearing 1,3-diphenyltriazenido ligands
1999, Journal of Organometallic Chemistry
Protonolysis reactions between tris(cyclopentadienyl)lanthanide complexes and 1,3-diphenyltriazene were investigated as routes to lanthanide complexes containing 1,3-diphenyltriazenido ligands. There was no detectable reaction between tris(cyclopentadienyl)erbium or tris(cyclopentadienyl)lutetium and excess 1,3-diphenyltriazene at ambient temperature in toluene solvent, due to the insolubility of the polymeric tris(cyclopentadienyl)lanthanide complexes in this medium. The monomeric, toluene-soluble adduct tris(cyclopentadienyl)(4-tert-butylpyridine)erbium(III) was obtained in 41% yield upon reaction of tris(cyclopentadienyl)erbium with 4-tert-butylpyridine in toluene at ambient temperature. Treatment of tris(cyclopentadienyl)(4-tert-butylpyridine)erbium or tris(cyclopentadienyl)(4-tert-butylpyridine)lutetium with 1,3-diphenyltriazene (one equivalent) in toluene at ambient temperature afforded bis(cyclopentadienyl)(1,3-diphenyltriazenido)(4-tert-butylpyridine)erbium(III) (73%) and bis(cyclopentadienyl)(1,3-diphenyltriazenido)(4-tert-butylpyridine)lutetium(III) (81%), respectively, as red–brown solids. Treatment of tris(cyclopentadienyl)lanthanide with 1,3-diphenyltriazene (three equivalents) and pyridine (two or three equivalents) in refluxing toluene afforded tris(1,3-diphenyltriazenido)bis(pyridine)erbium(III)·(pyridine)_1.0·(toluene)_0.5 (48%) and tris(1,3-diphenyltriazenido)bis(pyridine)lutetium(III) (63%) were isolated as red–brown solids. The crystal structures of bis(cyclopentadienyl)(1,3-diphenyltriazenido)(4-tert-butylpyridine)erbium(III) and tris(1,3-diphenyltriazenido)bis(pyridine)erbium(III)·(pyridine)_1.0·(toluene)_0.5 are described. Both complexes are monomeric and contain bidentate 1,3-diphenyltriazenido ligands. The potential utility of lanthanide complexes bearing 1,3-diaryltriazenido ligands as source compounds in chemical vapor deposition processes is discussed.
Molecular dynamics of N,N′-di-p-fluorophenyltriazenido complex of platinum(II)
1998, Inorganica Chimica Acta
The triazenide complex of Pt(II) trans-(o-Tol)Pt(PEt₃)₂N₃Ar₂(1) (Ar = p-FC₆H₄) was synthesized by reaction of (o-Tol)Pt(PEt₃)₂BF₄ with Ar₂N₃Na. The ¹H, ¹⁹F and ³¹P NMR spectra of this complex in toluene-d₈ were studied at different temperatures. Two kinds of dynamic processes were observed. The first one is the intramolecular N,N′ migration of the (o-Tol)Pt(PEt₃)₂ group, detected by ¹⁹F NMR. The second process, revealed by ¹H, ¹⁹P NMR, is the rotation around the partially double N(2)–N(3) bond. Thermodynamic parameters for these processes were calculated from dynamic NMR spectra.
Synthesis and characterization of titanium and zirconium complexes bearing diphenyltriazenido ligands
1997, Polyhedron
Treatment of tetrakis(dimethylamido)titanium(IV) and tetrakis(diethylamido)titanium(IV) with two equivalents of 1,3-diphenyltriazene in hexane afforded bis(dimethylamido)bis(1,3-diphenyltriazenido)titanium(IV) (62%) and bis(diethylamido)bis(1,3-diphenyltriazenido)titanium(IV) (68%), respectively, as deep red crystalline solids. Reaction of tetrakis(dimethylamido)titanium(IV) with more than two equivalents of 1,3-diphenyltriazene in refluxing toluene did not lead to substitution of more than two dimethylamido ligands, but only gave extensive decomposition. Treatment of tetrakis(dimethylamido) zirconium(IV) with four equivalents of 1,3-diphenyltriazene in hexane afforded tetrakis(1,3-diphenyltriazenido)-zirconium(IV) (79%) as a deep red crystalline solid. Crystal structures of bis(dimethylamido) tetrakis(1,3-diphenyltriazenido)zirconium(IV) were determined. The titanium complexes exhibit octahedral coordination spheres with cis-dialkylamido ligands, while the zirconium complex is eight-coordinate with η²-1,3-diphenyltriazenido ligands. Solution molecular weight measurements for tetrakis(1,3-diphenyltriazenido)zirconium(IV) indicated a monomeric structure in benzene, consistent with the structural results.

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The molecular and crystal structure of trans-hydridobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)platinum(II) [PtH(PPh3)2(p-CH3C6H4NNNC6H4CH3-p)]

Abstract

J. Organometal. Chem.

J. Organometal. Chem.

J. Chem. Soc.

The molecular and crystal structure of trans-hydridobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)platinum(II) [PtH(PPh₃)₂(p-CH₃C₆H₄NNNC₆H₄CH₃-p)]