Synthesis of tetrahedral mixed-metal clusters of the iron triad. Preparation and characterization of tridecacarbonyldihydroironosmiumdiruthenium and tridecacarbonyldihydroirondiosmiumruthenium

Abstract

Several new mixed-metal clusters of the Fe-Ru-Os triad have been prepared through the addition of carbonylmetalates to closed metal trimers. Addition of Na2[Fe(CO)4] to Ru2Üs(CO)i2 and RuOs2(CO)i2, followed by acidification, yielded Fl2FeRu20s(C0)i3 and H2FeRuOs2(CO)i3, the first examples of clusters comprised of three different transition metals. F)2Fe2Ru2(CO)i3 was prepared by allowing Na2[Fe(CO)4] to react with Fe2Ru(CO)i2 or by addition of [Ru(CO)4]2-to Fe3(CO)i2-Addition of [Ru(CO)4]2_ to Os3(CO)i2 or [Os(CO)4]2~t o Ru3(CO)¡2 gave an inseparable mixture of H4Ru4(CO)i2, H4Ru3Os(CO)12, H4Ru20s2(C0)12, H4RuOs3(CO)i2, and H4Os4(CO)i2. An improved synthesis of FFFe-Ru3(CO)i3 is reported and an alternative route to Fl2FeOs3(CO)i3 is described. The new clusters have been characterized by their NMR, infrared, electronic absorption, and mass spectra and the spectral evidence suggests tetrahedral structures similar to the known structures of H2FeRu3(CO)i3 and FI2Ru4(CO)i3.

Methanation of carbon monoxide and dioxide by supported metal carbonyl clusters

“…H2RuJ(C0)1j (16). HzFcRuI-(CO)lz ( 161, L(Ph,P)zNILC~R~I(CO)l.~l ( 17), and C O , ( C O )~~ ( 18) were prepared as in the literature.…”

The Hydrido‐Transition Metal Cluster Complexes

“…With due precautions regarding loss of hydrogen in ionization, reliable molecular weights are routinely obtained from parent ion peaks in the mass spectra of hydrido-metal cluster complexes (9,120,173,197). Hydrogen loss is not a significant problem when using chemical ionization mass spectrometry (120) or in conventional ionization mass spectrometry for compounds of the third row metals and/or for deuterio-metal clusters (9,173).…”

“…Hydrogen loss is not a significant problem when using chemical ionization mass spectrometry (120) or in conventional ionization mass spectrometry for compounds of the third row metals and/or for deuterio-metal clusters (9,173). Where an observed multiplet varies significantly from the intensity pattern expected from the natural abundance of the metal isotopes, the peaks can be deconvoluted using MASPAN, a computer program written by M. A. Andrews (173).…”

Substitution derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13: Monosubstituted group 15 derivatives

“…One interesting family of heteronuclear clusters is tetranuclear clusters of the formulae M 0 M 3 (l-H) 2 (CO) 13 , where M and M 0 are the group 8 elements; three members of this family are known, viz., FeRu 3 (l-H) 2 (CO) 13 , FeOs 3 (l-H) 2 (CO) 13 and RuOs 3 (l-H) 2 (CO) 13 (1); an unsuccessful attempts have also been made on the preparations of the remaining members of this series, viz., the clusters MFe 3 (l-H) 2 (CO) 13 (where M = Ru, Os) [1]. The chemistry of the first two members of this series has been fairly well investigated [2]; insofar as phosphine substitution chemistry is concerned, that of FeRu 3 (l-H) 2 (CO) 13 has been investigated in quite great detail by Geoffroy and coworkers [3].…”