ISSN:
0009-2940
Keywords:
Binuclear complexes
;
Molybdenum complexes
;
Rhodium complexes
;
Sulfur dioxide bridges
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Sulfur(IV) Compounds as Ligands, IX. - Binuclear Molybdenum-Rhodium Complexes with Sulfur Dioxide as a Bridging LigandThe hetero-binuclear complexes [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) and [MoRh(CN)(CO)3(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) are the first compounds which contain sulfur dioxide as a bridging ligand connected to two metal atoms from different groups of the periodic table. The synthesis starts from Mo(CO)3(NCMe)3 (7), which reacts with the chelating ligands Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm), and Ph2AsCH2AsPh2 (daam) to give the mononuclear precursors Mo(CO)3-(η2-Ph2E1CH2E3 Ph2)(η1-Ph2E2CH2E4 Ph2) (9-12). With [Rh2Cl2(CO)4] these are converted to the binuclear complexes [MoRhCl(CO)4(μ-Ph2E1CH2E3 Ph2)(μ-Ph2E2CH2E4Ph 2)] (15-18). Reversible CO/SO2 exchange finally gives 1-4 and the analogous bromide 5, the cyanide complex 6 is obtained from 1 and NaCN in liquid ammonia.
Notes:
Die heteronuklearen Zweikernkomplexe [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) und [MoRh(CN)(CO)3-(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) sind die ersten Verbindungen, in denen Schwefeldioxid als Brückenligand an zwei Metallatome aus verschiedenen Gruppen des Periodensystems gebunden ist. Die Synthese geht von Mo(CO)3(NCMe)3 (7) aus, das mit den Chelatliganden Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm) und Ph2AsCH2AsPh2 (daam) zu den einkernigen Vorstufen Mo(CO)3(η2-Ph2E1CH2E3 Ph2) (η1-Ph2E2CH2E4 Ph2) (9-12) umgesetzt wird. Daraus entstehen mit [Rh2Cl2(CC)4] die Zweikernkomplexe [MoRhCl(CO)4(μ-Ph2E1CH2E3Ph 2)(μ-Ph2E2CH2E4Ph2)] (15-18). Reversibler CO/SO2-Austausch ergibt schließlich 1-4 und das analoge Bromid 5, der Cyanokomplexe 6 wird aus 1 und NaCN in flüssigem Ammoniak erhalten.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19891220905
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