SYNTHESES AND X-RAY CRYSTAL-STRUCTURES OF DICHLOROBIS(TERT-BUTYLIMIDO) COMPLEXES OF MOLYBDENUM(VI) - POTENTIAL PRECURSORS TO MOLYBDENUM NITRIDE AND MOLYBDENUM CARBONITRIDE
Ht. Chiu et al., SYNTHESES AND X-RAY CRYSTAL-STRUCTURES OF DICHLOROBIS(TERT-BUTYLIMIDO) COMPLEXES OF MOLYBDENUM(VI) - POTENTIAL PRECURSORS TO MOLYBDENUM NITRIDE AND MOLYBDENUM CARBONITRIDE, Journal of the Chinese Chemical Society, 41(6), 1994, pp. 755-761
The bistertbutylimido complexes [MoCl(mu L-Cl)(NBu(t))(2)(NH(2)Bu(t))]
(2), 1, and MoCl2(NBu(t))(2)(py)(2), 2 (py = pyridine), were prepared
by reacting MoCl2(NBu(t))(2)(dme) (dme = dimethoxyethane) with excess
Bu(t)NH(2) and pyridine, respectively. Their structures were determine
d by X-ray crystallography. 1 has a pseudo edge-shared bioctahedral ge
ometry with two Cl ligands bridging the Mo centers unequally. Pertinen
t bond distances and angles for 1, Mo = NBu(bent)(t) = 1.737(3) Angstr
om, angle Mo = N-CMe(3) = 154.0(2)degrees; Mo = NBu(linear)(t) = 1.725
(3) Angstrom, angle Mo = N-CMe(3) = 172.4(2)degrees; Mo-Bu(t)NH(2) = 2
.233(2) Angstrom; Mo=Cl-bridging = 2.575(1) and 2.835(1) Angstrom, and
Mo-Cl-leminal = 2.428(1) Angstrom. Crystal data for 1: triclinic, spa
ce group P (1) over bar, a = 8.897(4) Angstrom, b = 10.518(3) Angstrom
, c = 10.663(3) Angstrom, alpha = 107.68(2)degrees, beta = 98.03(3)Ang
strom, gamma = 99.26(3)degrees, V = 919.3(5) Angstrom(3), Z = II D-c =
1.381 g/mL. 2 is mononuclear with a distorted octahedral geometry wit
h two trans Cl ligands, two cis-oriented Bu(t)N = ligands, and two py
ligands trans to the imido groups. Pertinent averaged bond distances a
nd angles for 2, Mo = NBu(bent)(t) = 1.736(4) Angstrom, angle Mo = N-C
Me, = 161.8(4)degrees; Mo = NBu(linear)(t) = 1.705(5) Angstrom, angle
Mo = N-CMe(3) = 173.4(4)degrees; Mo-N(py)= 2.44(1), Mo-Cl = 2.421(3) A
ngstrom Crystal data for 2: orthorhombic, space group Pna2(1) a = 16.8
60(2) Angstrom, b = 8.920(3) Angstrom, c = 15.120(3) Angstrom, V = 227
4.1(9) Angstrom(3), Z = 4, D-c = 1.362 g/mL. A potential application o
f 2 as a single-source precursor to grow molybdenum nitride and molybd
enum carbonitride thin films by low pressure chemical vapor deposition
(LPCVD) was explored. Cubic phase thin films (a(thin film) = 4.16 - 4
.20 Angstrom) were grown at temperatures between 450 degrees C and 650
degrees C with hydrogen as carrier gas. At 450 degrees C, thin films
of molybdenum nitride were obtained. With temperature of deposition in
creased from 450 degrees C to 650 degrees C, the ratio C/Mo increased
from 0.03 to 0.5 whereas the ratio C/Mo decreased from 0.7 to 0.3. Thu
s, thin films of molybdenum carbonitride were deposited at 650 degrees
C.