NEW METAL-CARBONYL-COMPLEXES OF MIXED GROUP-15 GROUP-16 ANIONS - STRUCTURAL CHARACTERIZATION OF [FE(AS3SE3)(2)(CO)](2-),[MN(AS3SE5)(CO)(3)](2-), AND [FE-2(ASTE4)(2)(CO)(4)](2-)/
Tm. Martin et al., NEW METAL-CARBONYL-COMPLEXES OF MIXED GROUP-15 GROUP-16 ANIONS - STRUCTURAL CHARACTERIZATION OF [FE(AS3SE3)(2)(CO)](2-),[MN(AS3SE5)(CO)(3)](2-), AND [FE-2(ASTE4)(2)(CO)(4)](2-)/, Inorganic chemistry, 34(17), 1995, pp. 4385-4391
The reactions of various mixed arsenic selenides and tellurides with m
etal carbonyls have been investigated. Several new clusters have been
isolated and stucturally characterized, Iron carbonyl reacts with As4S
e62- to form [Fe(As3Se3)(2)(CO)](2-), which contains two As3Se32- frag
ments attached to an Fe(CO) center. The compound is reminiscent of (an
d isoelectronic with) the previously reported [M(As3Se3)(2)(CO)(2)](2-
) (M = Mo, W). Crystallographic data: space group (P) over bar 1, a =
13.114(2) Angstrom, b = 19.250(2) Angstrom, c = 11.791(2) Angstrom, al
pha = 98.85(1)degrees, beta 108.81(1)degrees, gamma = 88.86(1)degrees,
V = 2782.7(7) Angstrom(3), Z = 2, R = 0.0721, R(w) = 0.0931. The same
main group cage also reacts with Mn-2(CO)(10) to form [Mn(As3Se5)(CO)
(3)](2-), which has a completely new topological framework. The struct
ure is based on the As4Se4 type with one As vertex replaced by a Mn(CO
)(3) fragment and the bound As containing a terminal As=Se bond. Cryst
allographic data: space group (P) over bar 1, a = 10.298(3) Angstrom,
b = 11.649(3) Angstrom, c = 24.950(6) Angstrom, alpha = 90.30(2)degree
s, beta = 94.32(2)degrees, gamma = 106.35(2)degrees, V = 2863(1) Angst
rom(3), Z = 2, R = 0.0464, R(w) = 0.0539. Iron carbonyl also reacts wi
th As2Te62- to form the first example of a transition metal arsenic te
lluride complex, [Fe-2(AsTe4)(2)(CO)(4)](2-). This dimer contains two
Fe(CO)(2) fragments linked by two unusual (Te-2)AsTe-Te ligands. Cryst
allographic data: space group C2/c, a = 11.268(4) Angstrom, b = 21.228
(9) Angstrom, c = 26.413(9) Angstrom, beta = 100.32(3)degrees, V = 621
6(4) Angstrom(3), Z = 4, R = 0.0646, R(w) = 0.0613. In addition to X-r
ay difffraction, these compounds were characterized by IR, far-IR, and
Se-77 and Te-125 NMR. A mote convenient preparation of the As2Te62- s
alt is also reported.