Preparation and Reactivity of Stannyl Complexes of Manganese and Rhenium

Abstract

The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C≡CH) yielded the trialkynylstannyl derivatives M[Sn(C≡CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C≡CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C≡CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)=O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate Re[SnH{OC(H)=O}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported

Stannyl Complexes of Rhodium and Iridium: Preparation of Mono‐ and Bis(trihydridestannyl) Derivatives

“…The use of NaBH 4 as a reagent to prepare tin trihydride complexes turns out to be an interesting synthetic method in tin chemistry that we had previously used to synthesise several [M]–SnH 3 derivatives ,,,,,,. In the present study, this route allowed the preparation of the first iridium complexes containing tin trihydride as a ligand.…”

“…In the present study, this route allowed the preparation of the first iridium complexes containing tin trihydride as a ligand. As observed with other stannyl derivatives,,,, the nature of the central metal and the ancillary ligands seem to be crucial for stabilising tin trihydride complexes. The pentamethylcyclopentadienyl half‐sandwich fragment with phosphite ligand is able to stabilise both mono‐ and bis(tin trihydride) derivatives, but only with iridium.…”

“…The IR spectra of the hydride‐trihydridestannyl complexes [IrH(SnH 3 )(η 5 ‐C 5 Me 5 ){P(OR) 3 }] ( 5 ) show one medium‐intensity band at 2113–2134 cm ‐1 attributed to the ν Ir‐H of the hydride and another one, of strong intensity and rather broad, at 1771–1755 cm ‐1 attributed to the stretching of the Sn–H bond of the SnH 3 ligand. However, two ν Sn‐H bands are expected for the metal‐bonded SnH 3 group, as had been observed in related Os and Re complexes ,. Probably, the difference of the stretching values of the two bands is too small to allow resolution by our instrument and therefore the spectra display only a single enlarged absorption.…”

Preparation of stannyl complexes of ruthenium and osmium stabilised by polypyridine and phosphite ligands

“…(14)(15)(16)(17) were only observed for ruthenium. All complexes were reddish-brown solids, stable in air and in solutions of organic solvents, where they behave as 1 : 1 electrolytes (11)(12)(13) or nonelectrolytes (14)(15)(16)(17). Analytical and spectroscopic data (IR and NMR) support the proposed formulation.…”

[Re(CO)3Cl(C5H4ClP)2] and [Re(CO)2Cl(C5H4ClP)3]: synthesis and characterization of two novel rhenium(i) phosphinine complexes

“…30 This difference indicates that phosphine ligands generally show p-bonding character, with phosphite ligands having a slightly more pronounced effect than phosphinine ligands.…”