The formal substitution of external C:C bonds in quinonoid hydrocarbons such as 7,7,8,8-tetraaryl-p-quinodimethanes and 1,1'-biphenyl-4,4'-diylbis(diarylmethyl) compds. with the isoelectronic B:N function has occurred in 1,4-bis(dimesitylboryl)-1,4-dihydropyrazine (1) and 1,1'-bis(dimesitylboryl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene (2). These new inorg. hybrid analogs of Thiele's and Chichibabin's hydrocarbons are sufficiently electron-rich to allow chem. and electrochem. one-electron oxidn. despite the strong p acceptor effect of BMes2 substituents. Unusually small 11B and 14N EPR/ENDOR coupling consts. of the cation radicals 1.bul.+ and 2.bul.+ indicate a considerable degree of p bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of p electron bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of p electron localization than Chichibabin's hydrocarbon. The B-N distance of 144.4 (3) pm is close to that in borazine or hexagonal boron nitride. Huckel MO calcns. were used to interpret EPR/ENDOR, electrochem., and structural results. on SciFinder(R)
%0 Journal Article
%1 Lichtblau.1993b
%A Lichtblau, Alexander
%A Hausen, Hans Dieter
%A Schwarz, Wolfgang
%A Kaim, Wolfgang.
%D 1993
%J Inorganic Chemistry
%K analog analog;crystal bipyridylidene boron boryl borylhydrobipyridylidene borylhydrobipyridylidene;electrochem borylhydrobipyridylidene;pyrazine borylhydropyrazine;mol hydro;Chichibabin hydro;Thiele hydrocarbon structure
%N 1
%P 73--78
%R 10.1021/ic00053a012
%T Inorganic hybrid analogs of Thiele's and Chichibabin's hydrocarbons. Spectroscopy, electrochemistry, and structure
%V 32
%X The formal substitution of external C:C bonds in quinonoid hydrocarbons such as 7,7,8,8-tetraaryl-p-quinodimethanes and 1,1'-biphenyl-4,4'-diylbis(diarylmethyl) compds. with the isoelectronic B:N function has occurred in 1,4-bis(dimesitylboryl)-1,4-dihydropyrazine (1) and 1,1'-bis(dimesitylboryl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene (2). These new inorg. hybrid analogs of Thiele's and Chichibabin's hydrocarbons are sufficiently electron-rich to allow chem. and electrochem. one-electron oxidn. despite the strong p acceptor effect of BMes2 substituents. Unusually small 11B and 14N EPR/ENDOR coupling consts. of the cation radicals 1.bul.+ and 2.bul.+ indicate a considerable degree of p bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of p electron bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of p electron localization than Chichibabin's hydrocarbon. The B-N distance of 144.4 (3) pm is close to that in borazine or hexagonal boron nitride. Huckel MO calcns. were used to interpret EPR/ENDOR, electrochem., and structural results. on SciFinder(R)
@article{Lichtblau.1993b,
abstract = {The formal substitution of external C:C bonds in quinonoid hydrocarbons such as 7,7,8,8-tetraaryl-p-quinodimethanes and 1,1'-biphenyl-4,4'-diylbis(diarylmethyl) compds. with the isoelectronic B:N function has occurred in 1,4-bis(dimesitylboryl)-1,4-dihydropyrazine (1) and 1,1'-bis(dimesitylboryl)-1,1',4,4'-tetrahydro-4,4'-bipyridylidene (2). These new inorg. hybrid analogs of Thiele's and Chichibabin's hydrocarbons are sufficiently electron-rich to allow chem. and electrochem. one-electron oxidn. despite the strong \textgreek{p} acceptor effect of BMes2 substituents. Unusually small 11B and 14N EPR/ENDOR coupling consts. of the cation radicals 1.bul.+ and 2.bul.+ indicate a considerable degree of \textgreek{p} bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of \textgreek{p} electron bonding within the B:N units. The crystal structure of 2 as bis(benzene) solvate reveals a significantly higher degree of \textgreek{p} electron localization than Chichibabin's hydrocarbon. The B-N distance of 144.4 (3) pm is close to that in borazine or hexagonal boron nitride. Huckel MO calcns. were used to interpret EPR/ENDOR, electrochem., and structural results. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Lichtblau, Alexander and Hausen, Hans Dieter and Schwarz, Wolfgang and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2df3efac867bb200f87ebc794b48d8787/b_schwederski},
doi = {10.1021/ic00053a012},
interhash = {9ff7ff1372ae0fda97f9e1645f16f00f},
intrahash = {df3efac867bb200f87ebc794b48d8787},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {analog analog;crystal bipyridylidene boron boryl borylhydrobipyridylidene borylhydrobipyridylidene;electrochem borylhydrobipyridylidene;pyrazine borylhydropyrazine;mol hydro;Chichibabin hydro;Thiele hydrocarbon structure},
number = 1,
pages = {73--78},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Inorganic hybrid analogs of Thiele's and Chichibabin's hydrocarbons. Spectroscopy, electrochemistry, and structure},
volume = 32,
year = 1993
}