Simple Os ca
rbyne complexes (HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
3, HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
2F, HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
2Cl, HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
2B
r, and CH
3C
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
3) a
re p
roduced in
reactions of lase
r-ablated Os atoms with small alkanes and methyl halides via oxidative C−H inse
rtion and α-hyd
rogen mig
ration. The diagnostic methylidyne C
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H st
retching abso
rptions of HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
3 and its halide de
rivatives a
re obse
rved about 200 cm
−1 above the p
recu
rso
r C
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H st
retching bands, and the f
requencies a
re consistent with s cha
racte
r in hyb
ridization in the C
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H bond. The methylidyne complexes all have computed
Cs st
ructu
res, and pa
rticula
rly the HC
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
3 and CH
3C
![]()
rc="http://pubs.acs.o
rg/images/entities/tbd1.gif">OsH
3 complexes have two equivalent sho
rte
r and one longe
r Os
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H bonds, pa
rallel to the case of Re in simila
r complexes. The st
rong unique Os
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H st
retching abso
rption at an exceptionally low f
requency is t
raced to the st
retching mode of the long Os
![]()
rc="http://pubs.acs.o
rg/images/entities/sbd_2.gif">H bond and antibonding cha
racte
r in the doubly occupied HOMO.