Advances in platinum metal carbonyls and their substituted derivatives. II. Rhodium, iridium, palladium and platinum carbonyls

Tripathi, Sunil Kumar; Srivastava, S. C.; Ramanathan, Mala; Shrimal, A.K.

doi:10.1016/s0020-1693(00)81992-1

Cited by 32 publications

(9 citation statements)

References 351 publications

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“…Iridium is hence found to form cationic, uncharged and with [Ir(CO) 3 ] 3- 33 also highly reduced carbonyl derivatives. As the oxidation state of the metal ranges from +3 to −3, ν̄(CO) values for terminal CO ligands range from a high of 2249 cm -1 for the A 1 mode in mer -Ir(CO) 3 (SO 3 F) 3 to a low of 1642 cm -1 for the [Ir(CO) 3 ] 3- anion…”

Section: Discussionmentioning

confidence: 99%

“…The sharp reduction in π-back-donation is evident from the long Ir-C bonds, ν j av (CO) of 2218 cm -1 , and the stretching force constant f r of 19.9 x 10 2 N m -1 . Iridium is hence found to form cationic, uncharged 32 and with [Ir(CO) 3 ] 3-33 also highly reduced carbonyl derivatives. As the oxidation state of the metal ranges from +3 to -3, ν j(CO) values for terminal CO ligands range from a high of 2249 cm -1 for the A 1 mode in mer-Ir(CO) 3 (SO 3 F) 3 to a low of 1642 cm -1 for the [Ir(CO) 3 ] 3anion.…”

Section: Discussionmentioning

confidence: 99%

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Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

et al. 1996

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Addition of carbon monoxide (0.5-2 atm) to iridium(III) fluorosulfate, Ir(SO(3)F)(3), dissolved in HSO(3)F over 4 days and at 60 degrees C, results in the quantitative formation of tris(carbonyl)iridium(III) fluorosulfate Ir(CO)(3)(SO(3)F)(3). Slow evaporation of the solvent produces single crystals of mer-Ir(CO)(3)(SO(3)F)(3). Crystal structure data for mer-Ir(CO)(3)(SO(3)F)(3): monoclinic, space group P2(1)/c, Z = 4, a = 8.476(1) Å, b = 12.868(2) Å, c = 12.588 (1) Å, beta = 108.24(1) degrees, V = 1304.0 Å(3), T = 200 K, R(F)() = 0.022 for 2090 data (I(o) >/= 2.5sigma(I(o))) and 200 variables. Vibrational spectra of the crystalline solid are consistent with a mer-isomer with CO stretching modes at 2249 (A(1)), 2208 (B(1)), and 2198 (A(1)) cm(-)(1) in the IR spectrum. In solution of HSO(3)F, additional CO stretching bands attributed to the fac-isomer are found in the FT-Raman and IR spectra at 2233 (A(1)) and 2157 cm(-)(1) (E). Additional evidence for a mixture of fac- and mer-isomers comes from (19)F NMR spectra. The vibrational spectra suggest strongly reduced iridium to CO pi-back-bonding. The crystal structure reveals significant intra- and intermolecular contacts between the electropositive C atom of the CO groups and O or F atoms of the fluorosulfate groups. Hence mer-tris(carbonyl)iridium(III) fluorosulfate becomes the first thermally stable, structurally characterized, and predominantly sigma-bonded carbonyl derivative of a metal in the +3 oxidation state.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

et al. 1996

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“…Even though cis -Pt(CO) 2 Cl 2 is known since 1868, its square planar coordination geometry 5 is limited in metal carbonyl chemistry − largely to halo carbonyl derivatives of various metal ions from the 4d and 5d series (Rh(I), Ir(I), Pd(II), Pt(II)) − with a d 8 configuration and to coordination compounds, which have a limited number of CO ligands. Of the halo carbonyl complexes, those of palladium and platinum have been widely studied, − mainly by Calderazzo and his group. − For homoleptic typical carbonyls 14-17 and highly reduced carbonylates, the square planar coordination geometry is unknown. All known tetracarbonyl species are invariably tetrahedral, − , including Pd(CO) 4 and Pt(CO) 4 , which exist in inert gas matrices only…”

Section: Introductionmentioning

confidence: 99%

Superelectrophilic Tetrakis(carbonyl)palladium(II)- and -platinum(II) Undecafluorodiantimonate(V), [Pd(CO)₄][Sb₂F₁₁]₂ and [Pt(CO)₄][Sb₂F₁₁]₂: Syntheses, Physical and Spectroscopic Properties, Their Crystal, Molecular, and Extended Structures, and Density Functional Calculations: An Experimental, Computational, and Comparative Study

et al. 2001

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The salts [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO(3)F)(6)], Pt(SO(3)F)(4) or PtF(6) in liquid SbF(5), or HF-SbF(5). The resulting moisture-sensitive, colorless solids are thermally stable up to 140 degrees C (M = Pd) or 200 degrees C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P2(1)/c (No. 14). The unit cell volume of [Pt(CO)(4)][Sb(2)F(11)](2) is smaller than that of [Pd(CO)(4)][Sb(2)F(11)](2) by about 0.4%. The cations [M(CO)(4)](2+), M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D(4)(h)() symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb(2)F(11)](-) anions in [M(CO)(4)][Sb(2)F(11)](2,) M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb-F-Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 - 0.37 A. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)(4)][Al(2)Cl(7)] are reported. The cations [Rh(CO)(4)](+) and [M(CO)(4)](2+), M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. (13)C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, reported here, allows a comparison to linear and octahedral [M(CO)(n)()][Sb(2)F(11)](2) salts [M = Hg (n = 2); Fe, Ru, Os (n = 6)] and their derivatives, which permit a deeper understanding of M-CO bonding in the solid state for superelectrophilic cations with [Sb(2)F(11)](-) or [SbF(6)](-) as anions.

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“…While three carbonyl chlorides of platinum(II), among them cis-Pt(CO),Cl,, are the very first transition metal carbonyl compounds to be reported (I), thermally stable, uncharged binary (homoleptic) carbonyls of platinum (2,3) as well as of palladium (2,4) and gold (5) are still unknown (6). Transient ' Author to whom correspondence may be addressed.…”

Section: Introductionmentioning

confidence: 99%

Homoleptic carbonyl cations of palladium(I), palladium(II), platinum(II), and gold(I)—simplified synthetic routes to their fluoroantimonate(V) salts

Siu¹,

Hwang²,

Aubke³

et al. 1996

Can. J. Chem.

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The original synthetic routes to the new noble metal carbonyl cations [Au(CO)2]+ and [M(CO)4]2+, M = Pd or Pt, as [Sb2F11]−salts are multi-step procedures that involve corrosive reagents and require commercially unavailable starting materials. We report here two general simplifications: (i) the sole use of liquid antimony(V) fluoride as reaction medium in a single-step carbonylation process, and (ii) the use of the commercially available chlorides AuCl3 and MCl2, M = Pd or Pt, as starting materials, in addition to the binary fluorosulfates Au(SO3F)3, Pd[Pd(SO3F)6], and Pt(SO3F)4. The simplified routes developed here for [Au(CO)2][Sb2F11] and [M(CO)4][Sb2F11]2, M = Pd or Pt, should make these new reagents more easily available for wider use in synthesis. In addition, these routes are found suitable for the generation of new carbonyl cations of electron-rich metals. Key words: metal carbonyl cations of Au(I), Pd(I), Pd(II), and Pt(II); solvolysis reactions in liquid SbF5, reductive carbonylation in liquid SbF5; carbonylations in strong acidic media.

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Advances in platinum metal carbonyls and their substituted derivatives. II. Rhodium, iridium, palladium and platinum carbonyls

Cited by 32 publications

References 351 publications

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Homoleptic carbonyl cations of palladium(I), palladium(II), platinum(II), and gold(I)—simplified synthetic routes to their fluoroantimonate(V) salts

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Advances in platinum metal carbonyls and their substituted derivatives. II. Rhodium, iridium, palladium and platinum carbonyls

Cited by 32 publications

References 351 publications

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)3(SO3F)3

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)3(SO3F)3

Homoleptic carbonyl cations of palladium(I), palladium(II), platinum(II), and gold(I)—simplified synthetic routes to their fluoroantimonate(V) salts

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Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃

Synthesis, Molecular Structure, and Vibrational Spectra of mer-Tris(carbonyl)iridium(III) Fluorosulfate, mer-Ir(CO)₃(SO₃F)₃