Carbonyl complexes of noble metals with halide ligands

Andreini, Bianca Patrizia; Dell’Amico, Daniela Belli; Calderazzo, Fausto; Venturi, Maria Giovanna; Pelizzi, Giancarlo; Serge, Annalaura

doi:10.1016/0022-328x(88)80661-2

Cited by 37 publications

(24 citation statements)

References 17 publications

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“…The crystal structure of Au(CO)Cl reveals that the molecules are arranged in head-to-tail antiparallel infinite chains with Au···Au contacts of 3.38 Å, similar to their isoelectronic RNCAu I Cl neutral isonitrile compounds, that have identical association of antiparallel chains . The stability of the halogen carbonyl complexes of Au(I) follows the same trend established earlier for palladium(II) and platinum(II), with the stability for all these complexes decreasing along the sequence Cl > Br > I. , One interesting IR characteristic in the Au(CO)Cl complex is the high ν C ⋮ O stretching vibrational frequency (2152−2162 cm -1 with some solvent dependence), which has been attributed to only modest π back-donation from the metal to the carbonyl group .…”

Section: Introductionsupporting

confidence: 65%

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

et al. 2007

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This work represents a synergistic experimental/computational study of the molecular spectroscopy and bonding in Au(CO)Cl in solution and the solid state. The luminescence behavior for crystalline solids is similar for Au(CO)Cl and related (RNC)AuCl complexes that likewise stack in infinite chains, and both exhibit orange-red unstructured phosphorescence bands with extremely large Stokes shifts ((15−20) × 103 cm-1). The long aurophilic distances computed for the ground state (∼3.2 Å) are contracted in the phosphorescent excited state (∼2.6 Å), demonstrating excimeric Au−Au covalent bonds. The spectral data suggest phosphorescent species in which the excimeric Au−Au bonding is extended beyond two adjacent molecules in the solid state. Controlling the concentration in frozen solutions attains phosphorescent bands due to dimeric species for which the emission energies are higher (in the blue region) than those for crystalline solids and are reproduced by ab initio calculations. The spectral findings herein suggest that predictive information about the supramolecular structure may be obtained by the luminescnce behavior. This is exemplified by crystals of (1,1,3,3-Me4BuNC)AuCl, whose red-orange luminsecence anticipated an extended-chain supramolecular structure, which was later verified crystallographically, as the molecules were found to pack in zigzag chains with alternating short (3.418 Å) and long (4.433 Å) aurophilic distances. Solutions of Au(CO)Cl exhibit negative deviation from Beer's law for, higher-energy monomer bands with the appearance of lower-energy bands at high concentrations due to the dimerization of molecules. Time-dependent density-functional theory (TD-DFT) calculations for monomer and dimer models show good agreement with the experimental spectra and account for the major absorption bands. Ab initio calculations (CCSD(T)/cc-pVTZ) show a blue shift of ∼23 cm-1 in the νC ⋮ O frequency upon complexation, thus providing the first computational evidence of this anomalous blue shift known experimentally for Au(CO)Cl.

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Section: Introductionsupporting

confidence: 65%

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

et al. 2007

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“…This fact seems to be logical, taking into account that the neutral nature of complex 7 and the presence of a good π acceptor ligand (CO) will reduce the π back-bonding from Pt(II) to the phosphine and the alkynyl ligand, in agreement with the observed spectroscopic facts for it. The Pt−C CO and C−O lengths are in the range of those found in other four-coordinate Pt(II) carbonyl complexes. − No lengthening of the CO bond as a consequence of the significant π back-donation to the terminal CO ligand, inferred from the low ν CO value, is observed.…”

Section: Resultsmentioning

confidence: 75%

“…Several spectroscopic facts concerning complex 7 are noteworthy. (a) The low value observed for the ν CO absorption (2079 cm -1 ) when compared with those of other neutral platinum(II) carbonyl complexes [103][104][105][106][107][108][109][110] suggests that the metal center in 7 is appreciably electron rich and that there is significant π backdonation to the terminal CO ligand. (b) The high wavenumbers for the ν CtC absorption (2127 cm -1 ) compared with those in the analogous complexes 8 and 9 and the notable shift of the C R resonance (101.85 ppm) to a higher field with respect to those in the starting complex, 2 (120.33 ppm, C R trans to P) indicate the scarce π back-bonding from Pt to the alkynyl ligand (in the remaining mononuclear complexes described in this paper, the C R resonance appears at a lower field than the C β resonance, but not in complex 7), this spectroscopic feature being commonly observed for the compounds cis-[Pt (C 6 57 [PtCu 2 (C 6 F 5 ) 2 (CtCR) 2 (acetone)] 2 , 30 and cis-[{Pt(C 6 F 5 ) 2 (µ-CtC t Bu) 2 }{Cu(bipy)} 2 ].…”

Section: Reactivity Of 2 Toward the Lewis Acid Species [Pt(c∧p)-(thf)...mentioning

confidence: 99%

“…The Pt-C CO and C-O lengths are in the range of those found in other four-coordinate Pt(II) carbonyl complexes. [103][104][105][106][107][108][109][110] No lengthening of the CO bond as a consequence of the significant π back-donation to the terminal CO ligand, inferred from the low ν CO value, is observed.…”

Section: Reactivity Of 2 Toward the Lewis Acid Species [Pt(c∧p)-(thf)...mentioning

confidence: 99%

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New Mono- and Polynuclear Alkynyl Complexes Containing Phenylacetylide as Terminal or Bridging Ligand. X-ray Structures of the Compounds NBu₄[Pt(CH₂C₆H₄P(o-tolyl)₂-κC,P)(C⋮CPh)₂], [Pt(CH₂C₆H₄P(o-tolyl)₂-κC,P)(C⋮CPh)(CO)], [{Pt(CH₂C₆H₄P(o-tolyl)₂-κC,P)(μ-C⋮CPh)}₂], and [{Pt(CH_2<

et al. 2007

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This work describes the synthesis of the compounds Q[Pt(C∧P)(C⋮CPh)2] (Q = Li+ (1), NBu4 + (2). C∧P = CH2C6H4P(o-tolyl)2-κC,P) and their use as precursors for the preparation of homo- and heteropolynuclear complexes by reactions with Lewis acid species of transition metals, M (M = Cu(I), Ag(I), Tl(I), Pd(II), Pt(II)). These reactions give rise to heteropolynuclear complexes that exhibit different bonding patterns for the bridging alkynyl ligands, depending on M. The reaction of 2 with readily available M+ (M = Cu, Ag) species affords the discrete tetranuclear clusters [{Pt(C∧P)(C⋮CPh)2M}2] (M = Cu (3), Ag (4)). The X-ray structure of 3 shows that in this complex both “Pt(C∧P)(C⋮CPh)2” fragments are connected by two d10 metal centers and are stabilized by alkynyl bridging ligands, showing the stronger preference of the MI centers (MI = Cu, Ag) for the electron-rich alkynyl units than for the basic Pt(II) center. However, the reaction of 2 with TlPF6 rendered the tentatively tetranuclear complex [{Pt(C∧P)(C⋮CPh)2Tl}2] (5), containing Pt→Tl dative bonds, which shows the higher affinity of thallium for the electron density of platinum(II) than for the alkynyl units. Moreover, the reaction of (NBu4)[Pt(C∧P)(C⋮CPh)2] (2) with the neutral complex [Pd(C6F5)2(THF)2] yields the compound (NBu4)[Pt(C∧P)(C⋮CPh)2Pd(C6F5)2] (11), in which the two alkynyl ligands are η2-bonded to Pd(II) in such a way that the “cis-Pt(C⋮CPh)2“ fragment acts as a chelate ligand toward Pd(II). Meanwhile the reactions with the cationic and neutral Pt(II) complexes [Pt(C∧P)(THF)2]+ and [Pt(C6F5)2(THF)2] produce the complexes [{Pt(C∧P)(μ-C⋮CPh)}2] (6) and (NBu4)[Pt(C∧P)(μ-C⋮CPh)2Pt(C6F5)2] (12), both containing the double μ2-η2(σ,π)-alkynyl bridging system “Pt2(μ-C⋮CPh)2” as a consequence of an alkynylating process. This bridging system “Pt2(μ-C⋮CPh)2” can be broken by neutral ligands, L, to give mono(σ-alkynyl) complexes of Pt(II). Thus, the complexes [Pt(C∧P)(C⋮CPh)L] (L = CO (7), py (8), tht (9), PPh3 (10)) have been obtained by reaction of 6 with L in a 1:2 molar ratio. When L = PPh3, the substitution reaction takes place with stereoretention, but not when L = CO, py, tht, as was conclusively established by an X-ray study on the complex [Pt(CH2C6H4P(o-tolyl)2)(CCPh)(CO)] (7). The cis or trans disposition of the two σ-C-donor ligands (C(C∧P), σ-C⋮CPh) around the Pt center in complexes 6−10 and 12 seems to depend as much on the transphobia of pairs of trans ligands (T) as on the steric requirements of those in the cis configuration.

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“…This is in fact the structure of the platinum analogue Pt 2 (CO) 2 I 4 isolated in a crystalline form and characterised by IR spectroscopy (n CO = 2122 cm 71 ) and X-ray diffraction data. 161 This is a dimer with a nonbonding metal ± metal spacing, two bridging iodide ligands, and two trans-disposed terminal carbonyl groups.…”

Section: Neutral and Anionic Palladium(+2) Carbonyl Halidesmentioning

confidence: 99%

Palladium carbonyl complexes

Stromnova¹,

Моисеев²

1998

Russ. Chem. Rev.

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Carbonyl complexes of noble metals with halide ligands

Cited by 37 publications

References 17 publications

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

Palladium carbonyl complexes

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Carbonyl complexes of noble metals with halide ligands

Cited by 37 publications

References 17 publications

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

Photophysics and Bonding in Neutral Gold(I) Organometallic Complexes with an Extended Aurophilic Supramolecular Structure

New Mono- and Polynuclear Alkynyl Complexes Containing Phenylacetylide as Terminal or Bridging Ligand. X-ray Structures of the Compounds NBu4[Pt(CH2C6H4P(o-tolyl)2-κC,P)(C⋮CPh)2], [Pt(CH2C6H4P(o-tolyl)2-κC,P)(C⋮CPh)(CO)], [{Pt(CH2C6H4P(o-tolyl)2-κC,P)(μ-C⋮CPh)}2], and [{Pt(CH2<

Palladium carbonyl complexes

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