Heteronuclear chains of four metal atoms including one quadruply bonded dimetal unit. Dichromium and dimolybdenum compounds with appended copper(I) atoms
Fa. Cotton et al., Heteronuclear chains of four metal atoms including one quadruply bonded dimetal unit. Dichromium and dimolybdenum compounds with appended copper(I) atoms, INORG CHEM, 39(8), 2000, pp. 1743-1747
It is shown that the M-2(DPhIP)(4) molecules (M = Cr, Mo; HDPhIP = 2,6-di(p
henylimino)piperidine) can each capture two Cu-I atoms to form molecules wi
th linear Cu ... M-M-4 ... Cn chains. In these chains the Cu-I atoms have o
nly weak interactions with the M atoms (Cr ... Cu = 2.628 Angstrom; Mo ...
Cu = 2.615 Angstrom) even though their introduction causes marked decreases
in the M-M-4 distances (from 2.265 to 1.906 Angstrom for Cr and from 2.114
to 2.078 Angstrom for Mo). These seemingly contradictory facts are explain
ed by noting that in the M-2(DPhIP)(4) molecules there are strong destabili
zing (to the M-M-4 bonds) donor interactions of the dangling nitrogen atoms
with the pi* orbitals. When these are eliminated by the introduction of th
e Cu-I atoms, the M-M-4 bonds become stronger and shorter.