Iron distannanes (η5-C5H5)Fe(CO)2SntBu2SntBu2X, (X=Cl, OMe): Thermal and photochemical transformations to iron stannylstannylenes

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η5-Me3SiC5H4)Fe(CO)[(SntBu2)2(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

“…The 119 Sn NMR of 5 exhibits two resonances at 251.2 ( 1 J 119Sn–119Sn = 1970 Hz; 1 J 119Sn–117Sn = 1925 Hz) and at 116.7 ppm, attributed to the α-Sn atom (Fe–Sn) and the β-Sn (Sn–Cl) atom, respectively. These data are comparable to the distannyliron complex 1 and are consistent with the trends observed in 29 Si NMR of iron-disilane complexes. , The monostannyliron complex 6 exhibits a single 119 Sn NMR resonance at 382.4 ppm, which is low field shifted in comparison with the α tin resonance of 5 due to substitution of the β tin atom with a chlorine atom. As expected, the 119 Sn NMR of 7 displays two resonances at 372.4 and 157.1 ppm due to two tin atoms in different environments involved in an iron–tin and tin–chlorine bond, respectively.…”

“…For 5 , an enantiomeric pair is found in the crystal structure, and the Sn–Cl bond is colinear with the Cp–Fe vector due to a hydrogen bond interaction with the Cp. The same conformation is observed in the analogue without the SiMe 3 substituent, and furthermore they can be described as isometric structures, showing that the Me 3 Si group has neither an electronic nor steric impact upon the structure . The Sn–Sn bond distance in 5 , 2.8733(7) Å, is also slightly longer than that reported in the Mo distannyl complex (η 5 -C 5 H 5 )­Mo­(CO) 3 ­Sn t Bu 2 Sn t Bu 2 Cl [2.8701(3) Å]…”

“…The tin–tin bond in distannyl complexes of the transition metals − undergoes various transformations, leading to reactive transition metal stannylene complexes, stannylene elimination reactions, and insertion of small molecules . They can also exhibit the oxidative addition of the tin–tin bond into low-valent electron-rich metal centers such as Pd and Pt .…”

“…Recently, we reported the synthesis, structural characterization, and photochemical/thermal reactivity of distannyl complexes of iron, FpSn t Bu 2 Sn t Bu 2 X (X = Cl, 1 ; OMe 2 ) [Fp = (η 5 -C 5 H 5 )­Fe­(CO) 2 )] including the formation of μ-X-stannyl­(stannylene)­iron complexes, via a stannyl­(stannylene)iron species formed by a 1,2-stannyl group migration to iron, Figure .…”

Heavy Tetrel Complexes of Ru Featuring Ru═E(R)X and Ru–E–R (E = Sn, Pb) Linkages

“…Silylene complexes have long been proposed as catalytic intermediates in important reactions such as silane redistribution − and hydrosilation. − A detailed understanding of the structures and reactivities of silylene complexes has been enhanced by investigations of the heavier congeners involving Ge, Sn, and Pb, which provide insights into multiple-bonding interactions between metals and group 14 elements and point to new reactivity patterns for unsaturated metal–main-group complexes. − …”