Carbonylchlorohydrotris(triphenylphosphine)osmium

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Carbonylchlorohydrotris (triphenylphosphine) osmium (II)
OsHClCOP3.svg
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Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 241-050-5
PubChem CID
  • InChI=1S/3C18H15P.CO.ClH.Os.H/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-2;;;/h3*1-15H;;1H;;/q;;;;;+2;-1/p-1
    Key: XUWSMTCLGDHTRB-UHFFFAOYSA-M
  • [H-].[C-]#[O+].C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.[Cl-].[Os+2]
Properties
OsHCl(CO)(PPh3)3
Molar mass 1041.6 g/mol
AppearanceWhite solid. [1]
Melting point 179-183°C
insoluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Carbonylchlorohydrotris(triphenylphosphine)osmium is a coordination complex with the formula OsHCl(CO)[P(C6H5)3]3. It contains four different ligands: hydride, carbon monoxide, chloride, and triphenylphosphine. As confirmed by X-ray crystallography, the complex has with meridional geometry (three phosphine ligands are coplanar) and the CO and Cl are mutually trans. [2]

Contents

Synthesis

It is prepared by heating ammonium hexachloroosmate(IV) with triphenylphosphine in boiling 2-(2-methoxyethoxy)ethanol. As described by the following idealized equation, the high boiling alcohol serves as a source of CO: [1]

(NH4)2OsCl6 + 4 P(C6H5)3 + 3 CH3OCH2CH2OCH2CH2OH → OsHCl(CO)[P(C6H5)3]3 + 2 NH4Cl + CH3OCH2CH2OCH2CH2O)2P(C6H5)3 + 3 HCl + CH3OCH2CH2OCH3

A similar but milder method (refluxing 2-methoxyethanol) employs formalin as a source of carbon monoxide. Again this complicated reaction is described by an idealized equation: [3]

Na2OsCl6 + H2O + CH2O + 4 (C6H5)3P → OsHCl(CO)[P(C6H5)3]3 + 2 HCl + OP(C6H5)3

It can also be prepared by reducing OsCl3(PPh3)3 with formaldehyde. [4]

Properties

It forms white crystalline prisms. It is insoluble in water, alcohols, and non-aromatic hydrocarbons, but moderately soluble in benzene, chloroform, dichloromethane, and acetone. When heated to its melting point in air, it reacts with oxygen and decomposes. In a sealed container of nitrogen it melts at 290°C with decomposition. The infrared spectrum shows a strong band at 2099 cm−1. [1] [3]

Reactions

It reacts with N-methyl-N-nitrosotoluene sulfonamide to yield the nitrosyl complex Os(NO)(CO)Cl(PPh3)2, which in turn can react with oxygen and triphenylphosphine to produce OsCl(NO)(PPh3)3. [4]

When treated with sodium hydroxide in a boiling solution of 2-methoxyethanol, it converts to the dihydride OsH2(CO)[P(C6H5)3]3 [3] :

OsHCl(CO)[P(C6H5)3]3 + NaOH + CH3OCH2CH2OH → OsH2(CO)[P(C6H5)3]3 + CH3OCH2CHO + NaCl + H2O

References

  1. 1 2 3 Chiririwa, Haleden; Muzenda, Edison (November 2014). "The Preparation and Characterisation of Osmium (IV), Osmium (II), and Osmium (0) Complexes from Refinery Materials" (PDF). International Conference on Chemical Engineering & Advanced Computational Technologies (ICCEACT): 32–35. Retrieved 17 July 2025.
  2. ↑ Gaydon, Quentin; Cassidy, Harrison; Kwon, Ohhyeon; Lagueux-Tremblay, Pierre-Louis; Bohle, D. Scott (2019). "Structural and spectroscopic trends in the phosphine Os(II) complexes OsHCl(CO)(L)(PPh3)2". Journal of Molecular Structure. 1192: 252–257. doi:10.1016/j.molstruc.2019.04.132.
  3. 1 2 3 Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley, M. F. (1974). Complexes of Ruthenium, Osmium, Rhodium, and Iridium Containing Hydride Carbonyl, or Nitrosyl Ligands. Inorganic Syntheses. Vol. 15. pp. 45–64. doi:10.1002/9780470132463.ch13. ISBN   978-0-470-13176-3.
  4. 1 2 Cotton, S. A. (1997). "Ruthenium and Osmium". Chemistry of Precious Metals (PDF). Rutland, UK: Blackie Academic & Professional. pp. xi, 67. Retrieved 17 July 2025.
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