SYNTHESIS AND SPECTROSCOPIC INVESTIGATIONS OF ORGANOALUMINUM DERIVATIVES OF ((DIMETHYLAMINO)METHYL)FERROCENE - CRYSTAL AND MOLECULAR-STRUCTURES OF ME3AL-CENTER-DOT-N(ME2)CH2C5H4FECP AND [(2-C4H3S)2AL-CENTER-DOT-N(ME2)CH2C5H4FECP]2O
R. Kumar et al., SYNTHESIS AND SPECTROSCOPIC INVESTIGATIONS OF ORGANOALUMINUM DERIVATIVES OF ((DIMETHYLAMINO)METHYL)FERROCENE - CRYSTAL AND MOLECULAR-STRUCTURES OF ME3AL-CENTER-DOT-N(ME2)CH2C5H4FECP AND [(2-C4H3S)2AL-CENTER-DOT-N(ME2)CH2C5H4FECP]2O, Inorganic chemistry, 33(6), 1994, pp. 1103-1108
The reaction of organoaluminum derivatives, R3Al (R = Me, Et, Ph), wit
h ((dimethylamino)methyl)ferrocene yields R3Al-N(Me2)CH2C5H4FeCp (R =
Me (1a), Et (1b), Ph (1c); Cp = C5H5) quantitatively. The alkoxo and t
hiolato complexes, [Me2Al(mu-OC6F5)]2 and [Me2Al(mu-C10H7-2-S)]n, also
react with ((dimethylamino)methyl)ferrocene to give Me2(C6F5O)Al.N(Me
2)CH2C5H4FeCp (2) and Me2(C10H7-2-S)Al.N(Me2)CH2C5H4FeCp (3), respecti
vely. Under similar reaction conditions ((dimethylamino)methyl)ferroce
ne does not react with tris(2,4,6-trimethylphenyl)aluminum (MeS3Al). T
he reaction of (2-C4H3S)3Al.OEt2 with the hydrated amine gives an alum
inoxane [(2-C4H3S)2Al.N(Me2)CH2C5H4FeCP]2O (4). The resulting compound
s have been characterized by H-1 and C-13 NMR spectroscopy. A single-c
rystal X-ray study of 1a established that it crystallizes in the monoc
linic cell system, space group P2(1)/a (No. 14), with cell constants o
f a = 12.969(2) angstrom, b = 13.103(2) angstrom, c = 20.411(3) angstr
om, beta = 91.45(2)-degrees, and Z = 8; R = 5.4% and R(w) = 3.7%, base
d on 2798 observed reflections (I(o) greater-than-or-equal-to 2.5sigma
(I)). The molecular unit is monomeric with an Al-N bond distance of 2.
06 angstrom. Compound 4 crystallizes in the monoclinic space group P2(
1)/n (No. 14), with cell constants of a = 11.518(2) angstrom, b = 13.1
26(2) angstrom, c = 13.839(3) angstrom, beta = 96.14(1)-degrees, and Z
= 2; R = 5.1% and R(w) = 5.0%, based on 2445 observed reflections (I(
o) greater-than-or-equal-to 2.5sigma(I)). The molecular unit consists
of two ferrocene moieties connected via an N-Al-O-Al-N linkage with Al
-N and Al-O bond distances of 2.024 and 1.690 angstrom respectively. T
he NMR spectra of la and 4 are temperature dependent with significant
changes occurring for the resonances associated with the Me2NCH2C5H4Fe
Cp group.