615570-84-8

Upstream product

• 14243-64-2 (triphenylphosphine)gold(I) chloride 
• 431899-38-6 [bis(triphenylphosphane)iminium][Os3(μ-PPh2)(CO)10] 
• 80984-33-4 Os₃(CO)11(PH(C₆H₅)2) 

Relevant academic research and scientific papers

Reaction of metallophosphanide anions with MLnX (X = halide) species as a simple route to heterometallic transition metal complexes

The reaction of metallophosphanides with MLnX leads to the formation of mixed-metal clusters via complexes that consist of a metallophosphine coordinated through the lone pair on the phosphorus atom to another metal fragment. This synthetic strategy has been employed to initially form trinuclear complexes with the general formula [(Ph2PML n)(OC)2Co(μ-DMAD)Mo(CO)2Cp] (MLn = Mn(CO)5 3, WCp(CO)2 4, FeCp(CO)2 5; DMAD = dimethylacetylene-dicarboxylate) from the reaction of the anion [(Ph 2P)(OC)2Co(n-DMAD)Mo(CO)2Cp]-, 2, with metal halide complexes, MLnX (X = Cl, Br). The complexes 3, 4 and 5 have been characterised spectroscopically, and an X-ray crystal structure of 5 shows that the Ph2PFe(CO)2Cp unit has coordinated to the cobalt centre through the lone pair on the phosphorus centre. Subsequent heating of 3 leads to carbonyl loss, and metal-metal bond formation, to yield [(OC)6CpCoMnMo(μ-CO)(μ-PPh2)(μ3- η2(II)-DMAD)], 6. An X-ray structure determination of 6 confirms that it contains a 'closed' metal triangle. In a related series of reactions the cluster anion [Os3(CO)10(μ-PPh2)] - was treated with a variety of metal-containing synthons, ML nX. With [FeCp(CO)2Cl] the cluster [Os3(CO) 10FeCp(CO)(μ-PPh2)(μ-CO)] 9 was obtained in good yield, and has been shown crystallographically to consist of an osmium triangle 'spiked' by an iron atom, with the Os-Fe bond bridged by the PPh2 group and a carbonyl ligand. With [(Ph3P)MCl] (M = Ag, Au) the tetranuclear 'butterfly' clusters [Os3(CO)10(μ-PPh 2)(μ-MPR3)] (10: M = Au, R = Ph; 11: M = Ag, R = Me) are obtained. These two complexes have been characterised spectroscopically and crystallographically.

Synthesis of novel mixed metal cluster complexes of osmium and mercury: Formation of the wheel-shaped cluster complexes Os6(μ-6-Hg)(μ-PR2)2(CO)20 (R = Ph, i-Bu)

The reaction of [PPN] [Os3(μ-PR2)(CO)10] (R = Ph 1a, i-Bu 1b) with HgCl2 in THF at -90 °C under exclusion of light gave the spirocyclic cluster μ4-Hg[Os3(μ-PR2)(μ-CO)(CO)9 ]2 (R = Ph 2a, i-Bu 2b). In these compounds the μ4-Hg bridges one Os-Os edge of each Os3 subunit. The remaining four edges are bridged by the μ-CO and μ-PPh2 ligands, respectively. 13C NMR spectra of 13CO-enriched 2a recorded at room temperature indicate an intramolecular rotation of the Os3 subunits around the axis running through the mercury atom and the midpoints of the Os-Os vectors it bridges. When 2a is heated in toluene or 1,4-dioxane, a rearrangement of the metal skeleton takes place. The μ4-Hg moiety is shifted to another edge of one of the Os3 rings, giving the isomer (CO)10(μ-PPh2)Os3(μ4-Hg)Os 3(μ-PPh2)(μ-CO)-(CO)9, 3a. The kinetics of this process were measured by UV/vis spectroscopy at four different temperatures in toluene and 1,4-dioxane, respectively. The reaction is of first order with a rate constant of 6.66(2) × 10-5 s-1 in toluene at 331.6(1) K. The thermodynamic parameters ΔH? = 97(5) kJ mol-1, ΔS? = -33(13) J K-1 mol-1, and ΔG? = 107(6) kJ mol-1 were derived from an Eyring plot. The analogous cluster complex 3b with μ-P(i-Bu)2 bridges has been obtained, too. Its structure has been confirmed by single-crystal X-ray analysis. 2a and 2b are highly photosensitive in solution. Upon exposure to daylight, they rearrange to give the novel wheel-shaped cluster complexes OS6(μ6-Hg)(μ-PR2)2(CO)20 (R = Ph 4a, i-Bu 4b). The structure of 4a was confirmed by single-crystal X-ray analysis. In 4a the Hg atom is located at the center of a Os6 ring. The ring is corrugated with the mercury atom in bonding distance to all osmium atoms. The course of the reaction was monitored for the conversion of 2a by UV/vis spectra exhibiting two isosbestic points indicating an intramolecular reaction.