61301-84-6Relevant academic research and scientific papers
SIX- AND SEVEN-COORDINATE MAIN GROUP IV METAL DERIVATIVES OF PENTACARBONYLVANADATE(3-) ION. STRUCTURAL CHARACTERIZATION OF TETRAETHYLAMMONIUM BIS(TRIPHENYLSTANNYL)PENTACARBONYLVANADATE
Ellis, John E.,Hayes, Thomas G.,Stevens, Robert E.
, p. 191 - 209 (2007/10/02)
Organotin and triphenyllead derivatives (Ph3Sn)2V(CO)5-, ((C6H11)3Sn)(Ph3Sn)V(CO)5-, (Me3Sn)(Ph3Sn)V(CO)5- and (Ph3Pb)2V(CO)5- containing seven-coordinate vanadium have been isolated as tetraethylammonium salts in 40-80percent yields from the reactions of appropriate organometal halides with Ph3EV(CO)52- (E=Sn, Pb).The latter have been prepared by the reduction of and are the first reported organotin and -lead metal carbonyl derivatives which contain a transition metal in a formal negative oxidation state.The crystal structure of , which is synthesized in low yields (ca. 15percent) from the photolysis of in the presence of Ph6Sn2, has been determined by single crystal X-ray diffraction techniques.The anion contains two Sn-V bonds with a Sn-V-Sn angle of 137.9(1) deg.Its geometry is discussed in terms of three possible seven-coordination environments.
Highly Reduced Organometallics. 4. Syntheses and Chemistry of Pentacarbonylvanadate(3-) Ion, V(CO)53-
Ellis, John E.,Fjare, Kristi Lenz,Hayes, Thomas G.
, p. 6100 - 6106 (2007/10/02)
Alkali-metal reductions of various salts containing V(CO)6- in liquid ammonia provide high yields of the super-reduced species V(CO)53- which contains vanadium in its lowest known formal oxidation state.Although salts of V(CO)53- containing lithium, sodium, and various onium cations rapidly decompose above 0 deg C, the trianion has been isolated and characterized as rather thermally stable rubidium and cesium salts, Rb3V(CO)5 and Cs3V(CO)5.A treacherously shock sensitive potassium salt, K3V(CO)5, is also described.Treatment of liquid ammonia solutions of Na3V(CO)5 with bis(triphenylphosphin)iminium chloride and tetraphenylphosphonium chloride provides thermally unstable, ammonia-insoluble solids believed to contain V(CO)53-.These decompose on warming to room temperature to provide V(CO)5PPh3-.Main-group 4 electrophiles, including R3EX (R = alkyl, aryl; E = Sn, Pb; X = halide), react with V(CO)53- to provide moderate to high yields of the new organometallic derivatives, (R3Sn)V(CO)52- and (R3E)2V(CO)51-.The dianions are the first reported organotin derivatives containing a transition metal in a formally negative oxidation state.Reactions of V(CO)53- in liquid ammonia with weak Broensted acids including water, ammonium cation, and acetonitrile are also described.High yields (85 - 95percent) of V(CO)5NH3- are obtained by treatment of V(CO)53- in liquid ammonia with 2 or more equiv of ammonium chloride.This amine-substituted anion is quite unstable in solution at room temperature but may be isolated as thermally stable Ph4As+ or Ph4P+ salts.
