0000000000137020
AUTHOR
Jeremy D. Erickson
Reactions of m-Terphenyl-Stabilized Germylene and Stannylene with Water and Methanol: Oxidative Addition versus Arene Elimination and Different Reaction Pathways for Alkyl- and Aryl-Substituted Species
Reactions of the divalent germylene Ge(ArMe6)2 (ArMe6 = C6H3-2,6-{C6H2-2,4,6-(CH3)3}2) with water or methanol gave the Ge(IV) insertion product (ArMe6)2Ge(H)OH (1) or (ArMe6)2Ge(H)OMe (2), respectively. In contrast, its stannylene congener Sn(ArMe6)2 reacted with water or methanol to produce the Sn(II) species {ArMe6Sn(μ-OH)}2 (3) or {ArMe6Sn(μ-OMe)}2 (4), respectively, with elimination of ArMe6H. Compounds 1–4 were characterized by IR and NMR spectroscopy as well as by X-ray crystallography. Density functional theory calculations yielded mechanistic insight into the formation of (ArMe6)2Ge(H)OH and {ArMe6Sn(μ-OH)}2. The insertion of an m-terphenyl-stabilized germylene into the O–H bond was…
Mechanistic Study of Stepwise Methylisocyanide Coupling and C-H Activation Mediated by a Low-Valent Main Group Molecule
An experimental and DFT investigation of the mechanism of the coupling of methylisocyanide and C-H activation mediated by the germylene (germanediyl) Ge(Ar(Me6))2 (Ar(Me6) = C6H3-2,6(C6H2-2,4,6-Me3)2) showed that it proceeded by initial MeNC adduct formation followed by an isomerization involving the migratory insertion of the MeNC carbon into the Ge-C ligand bond. Addition of excess MeNC led to sequential insertions of two further MeNC molecules into the Ge-C bond. The insertion of the third MeNC leads to methylisocyanide methyl group C-H activation to afford an azagermacyclopentadienyl species. The X-ray crystal structures of the 1:1 (Ar(Me6))2GeCNMe adduct, the first and final insertion …
Reactions of m-Terphenyl-Stabilized Germylene and Stannylene with Water and Methanol: Oxidative Addition versus Arene Elimination and Different Reaction Pathways for Alkyl- and Aryl-Substituted Species
Reactions of the divalent germylene Ge(ArMe6)2 (ArMe6 = C6H3-2,6-{C6H2-2,4,6-(CH3)3}2) with water or methanol gave the Ge(IV) insertion product (ArMe6)2Ge(H)OH (1) or (ArMe6)2Ge(H)OMe (2), respectively. In contrast, its stannylene congener Sn(ArMe6)2 reacted with water or methanol to produce the Sn(II) species {ArMe6Sn(μ-OH)}2 (3) or {ArMe6Sn(μ-OMe)}2 (4), respectively, with elimination of ArMe6H. Compounds 1–4 were characterized by IR and NMR spectroscopy as well as by X-ray crystallography. Density functional theory calculations yielded mechanistic insight into the formation of (ArMe6)2Ge(H)OH and {ArMe6Sn(μ-OH)}2. The insertion of an m-terphenyl-stabilized germylene into the O–H bond was…
CCDC 1431125: Experimental Crystal Structure Determination
Related Article: Jeremy D. Erickson, Petra Vasko, Ryan D. Riparetti, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2015|Organometallics|34|5785|doi:10.1021/acs.organomet.5b00884
CCDC 954558: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553
CCDC 1431127: Experimental Crystal Structure Determination
Related Article: Jeremy D. Erickson, Petra Vasko, Ryan D. Riparetti, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2015|Organometallics|34|5785|doi:10.1021/acs.organomet.5b00884
CCDC 1431126: Experimental Crystal Structure Determination
Related Article: Jeremy D. Erickson, Petra Vasko, Ryan D. Riparetti, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2015|Organometallics|34|5785|doi:10.1021/acs.organomet.5b00884
CCDC 954559: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553
CCDC 954557: Experimental Crystal Structure Determination
Related Article: Zachary D. Brown , Petra Vasko , Jeremy D. Erickson , James C. Fettinger , Heikki M. Tuononen , and Philip P. Power|2013|J.Am.Chem.Soc.|135|6257|doi:10.1021/ja4003553
CCDC 1431124: Experimental Crystal Structure Determination
Related Article: Jeremy D. Erickson, Petra Vasko, Ryan D. Riparetti, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2015|Organometallics|34|5785|doi:10.1021/acs.organomet.5b00884