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First Hyperpolarizabilities of Manganese(I)−Chromium(0) Sesquifulvalene Complexes
Author(s) -
Tamm Matthias,
Bannenberg Thomas,
Baum Kim,
Fröhlich Roland,
Steiner Thomas,
MeyerFriedrichsen Timo,
Heck Jürgen
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200006)2000:6<1161::aid-ejic1161>3.0.co;2-y
Subject(s) - chemistry , manganese , chromium , inorganic chemistry , organic chemistry
The synthesis of monometallic manganese and bimetallic manganese−chromium complexes incorporating the sesquifulvalene derivatives 2‐(2,4,6‐cycloheptatrien‐1‐ylidene)indene ( VI ) and [(2,4,6‐cycloheptatrien‐1‐ylidene)ethenylidene]cyclopentadiene ( VII ) is reported. Charge separation is observed upon complexation and stabilization of VI and VII by metal centers, and the spectroscopic and structural properties of [( VI )Mn(CO) 3 ]BF 4 ( 6 ), [(OC) 3 Mn(μ‐ VI )Cr(CO) 3 ]BF 4 ( 8 ), [( VII )Mn(CO) 3 ]BF 4 ( 13 ), and [(OC) 3 Mn(μ‐ VII )Mn(CO) 3 ]BF 4 ( 15 ) are clearly indicative of sesquifulvalene ligands coordinated in a dipolar η 5 or μ‐η 5 :η 7 fashion, respectively. The coplanar cyclopentadienyl and cycloheptatrienyl fragments act as strongly coupled electron‐donating and ‐accepting groups and strong negative solvatochromism is observed for complexes 6 , 8 , 13 , and 15 . Accordingly, exceptionally large first molecular hyperpolarizabilities β have been determined by means of hyper Raleigh scattering for the bimetallic species 8 and 15 , as well as for some related compounds. The X‐ray crystal structures of anti ‐[(OC) 3 Mn(μ‐η 5 :η 7 ‐ VI )Cr(CO) 3 ] ( 8 ) and syn ‐[(OC) 3 Mn(μ‐η 5 :η 7 ‐ VII )Cr(CO) 3 ] ( 15 ) are reported.