Synthesis, characterization and Twin Polymerization of a novel dioxagermine

Zirconium and Hafnium Twin Monomers for Mixed Oxides

“…This concept was recently extended to transition-metal-containing monomers from titanium and tungsten [20][21][22][23] and was also adapted to tin and germanium. [24][25][26][27] …”

Tin Nanoparticles in Carbon/Silica Hybrid Materials by the Use of Twin Polymerization

“…However, organotin compounds such as those used in the study (tributylphenyltin or tributylstannane) should be avoided in future industrial applications because of their toxic nature. [14][15][16][17][18][19][20] The different materials are cross-linked in the hybrid material, which prevents phase separation and leads to bicontinuous networks with domain sizes of a few nanometers. Previously, the preparation of hybrid materials composed of tin oxide, silica, and a phenolic resin by the use of the simultaneous twin polymerization route starting from novel tin(IV) alkoxides was reported.…”

Chiral Spirocyclic Germanium Thiolates - An Evaluation of Their Suitability for Twin Polymerization based on A Combined Experimental and Theoretical Study

“…[17] The Ge-O benzylic bond lengths of thiolate 2 (1.744(2) and 1.7657 (19) ) and the Ge-O phenolate distances of R a -3 (1.767 (5) and 1.775 (5) ) and S a -3 (1.783(4) and 1.784(4) ) are slightly shorter than the values reported for 6-bromo-2,2-ditert-butyl-4H-1,3,2-benzo[d]dioxagermine (Ge-O benzylic 1.7846 (18) and Ge-O phenolate 1.8168 (17) ). [18] However, the germanium oxygen bond lengths are within the typical range (1.749(3) -1.849(2) ) as reported for germanium(IV) alkoxides such as LGe(O i Pr)·(HO i Pr) (L = 6,6',6''-(nitrilotris(methylene))tris(2,4-dimethylphenolate)), [19] GeL 2 (L = [1,1'-bi(cyclohexane)]-1,1'-bis(olate)) [20] and [2,2'-Se(4,6-di-tert-butyl-C 6 H 2 O) 2 ] 2 Ge. [21] The Ge-S benzenethiolate and the Ge-S benzylic distances in 2, R a -3 and S a -3, respectively, are significantly shorter than the corresponding bond lengths (DGe-S benzenethiolate % 0.04 and DGe-S benzylic % 0.03 ) as determined for compound 1.…”

“…The Ge‐S benzylic bond lengths (2.1836(5) Å and 2.1969(5) Å for 1 ; 2.157(2) Å and 2.164(2) Å for R a ‐ 3 ; 2.167(2) Å and 2.1707(19) Å for S a ‐ 3 ) and the Ge‐S benzenethiolate distances (2.2292(5) Å and 2.2270(5) Å for 1 ; 2.1910(7) Å and 2.1956(7) Å for 2 ) are in agreement with values reported for the structurally related 2,2’‐spirobi[benzo[ d ][1,3,2]dithiagermole] (Ge−S 2.195(2) – 2.199(2) Å) and other germanium thiolates exhibiting tetrahedral coordination of the germanium atom such as tetrakis(phenylthio)germane (Ge−S 2.2149(6) – 2.2191(5) Å) and tetrakis( p ‐tolylthio)germane (Ge−S 2.211(1) – 2.221(1) Å) . The Ge‐O benzylic bond lengths of thiolate 2 (1.744(2) Å and 1.7657(19) Å) and the Ge‐O phenolate distances of R a ‐ 3 (1.767(5) Å and 1.775(5) Å) and S a ‐ 3 (1.783(4) Å and 1.784(4) Å) are slightly shorter than the values reported for 6‐bromo‐2,2‐di‐ tert ‐butyl‐4 H ‐1,3,2‐benzo[ d ]dioxagermine (Ge‐O benzylic 1.7846(18) Å and Ge‐O phenolate 1.8168(17) Å) . However, the germanium oxygen bond lengths are within the typical range (1.749(3) Å – 1.849(2) Å) as reported for germanium(IV) alkoxides such as LGe(O i Pr)⋅(HO i Pr) (L = 6,6′,6′′‐(nitrilotris(methylene))tris(2,4‐dimethylphenolate)), GeL 2 (L = [1,1′‐bi(cyclohexane)]‐1,1′‐bis(olate)) and [2,2’‐Se(4,6‐di‐ tert ‐butyl‐C 6 H 2 O) 2 ] 2 Ge .…”

“…The presence of these signals is indicative for the formation of quinone methides and ortho ‐cresol that have been identified as reactive intermediates in the process of thermally induced TP for precursor A . Note that quinone methide formation was also observed upon heating of 6‐bromo‐2,2‐di‐ tert ‐butyl‐4 H ‐1,3,2‐benzo[ d ]dioxagermine, which is structurally related to compound 3 but contains only one salicyl alcoholate moiety . Thermogravimetric analysis in combination with mass spectrometry (TGA‐MS) confirmed the formation of quinone methides and ortho ‐cresol as volatile byproducts upon heating of thiolate 3 (Figure S5).…”