Preparation and reactions of water stable hypervalent 10‐Sn‐5 allyl ate complexes

The synthesis and structure of a dianionic species with a bond between pentacoordinated tin atoms: bonding properties of the tin–tin bond

“…The 119 Sn chemical shift of 7 is reasonable for an anionic pentacoordinated tin nucleus coordinated by electron-withdrawing ligands as it is similar to other pentacoordinated tin allyl ate complexes, e.g. 38 The 119 Sn-117 Sn coupling constant ( 1 J (Sn-Sn) = 15 532 Hz) of 7 is similar to those of neutral pentacoordinated distannanes, e.g. Ph 4 Sn 2 (OOCCH 3 ) 2 1 [ 1 J (Sn-Sn) = 16 120 Hz], 31 but is much larger than those of distannanes, such as Ph 3 Sn-SnPh 3 ( 1 J (Sn-Sn) = 4281 Hz) and (t-Bu)(i-Pr) 2 Sn-Sn(t-Bu)(i-Pr) 2 ( 1 J (Sn-Sn) = 764 Hz).…”

“…(n-Et 4 N) + [(1,2-C 6 H 4 C(CF 3 ) 2 O-) 2 Sn(CH 2 CHCH 2 )] − (δ Sn −105.0 ppm). 38 The 119 Sn-117 Sn coupling constant ( 1 J (Sn-Sn) = 15 532 Hz) of 7 is similar to those of neutral pentacoordinated distannanes, e.g. Ph 4 Sn 2 (OOCCH 3 ) 2 1 [ 1 J (Sn-Sn) = 16 120 Hz], 31 but is much larger than those of distannanes, such as Ph 3 Sn-SnPh 3 ( 1 J (Sn-Sn) = 4281 Hz) and (t-Bu)(i-Pr) 2 Sn-Sn(t-Bu)(i-Pr) 2 ( 1 J (Sn-Sn) = 764 Hz).…”

“…A reason for this is simply not ascribed to the instability of the ate-type structure of each tin atom as several stable pentacoordinated ate-type tin compounds, which show a trigonal bipyramidal (TBP) structure around the tin atom, have been synthesized by taking advantage of electron-withdrawing bidentate ligands. 7,[37][38][39][40] We previously reported the synthesis of disilicate 5 41,42 and digermanate 6, 43 which are dianionic species containing a bond between two pentacoordinated ate-type silicon and germanium atoms, respectively. A tin analogue of 5 and 6 could be a challenging synthetic target considering the much smaller bond energy of the Sn-Sn bond in comparison to the Si-Si and Ge-Ge bonds.…”