INTRAMOLECULAR VS INTERMOLECULAR ALPHA-HYDROGEN ABSTRACTION IN THE GENERATION OF MULTIPLE IMIDO COMPLEXES - SYNTHESIS, REACTIVITY, AND STRUCTURAL STUDIES OF THE D(0) TRIS(IMIDO) FUNCTIONAL-GROUP OF TUNGSTEN
Dl. Morrison et al., INTRAMOLECULAR VS INTERMOLECULAR ALPHA-HYDROGEN ABSTRACTION IN THE GENERATION OF MULTIPLE IMIDO COMPLEXES - SYNTHESIS, REACTIVITY, AND STRUCTURAL STUDIES OF THE D(0) TRIS(IMIDO) FUNCTIONAL-GROUP OF TUNGSTEN, Organometallics, 14(5), 1995, pp. 2435-2446
The synthesis, reactivity, and structural characterization of the d(0)
tris(imido)complex [Li(THF)(4)][W(NAr)(3)Cl] (2, Ar = 2,6-C6H3-i-Pr-2
) are reported. When W(NAr)Cl-4(THF) reacts with 2 equiv of Me(3)SiNHA
r in THF, the bis(imido) compound W(NAr)(2)Cl-2(THF)(2) (1) is isolate
d. Reacting W(NAr)(2)Cl-2(THF)(2) with 2 equiv of LiNHAr in THF afford
s the yellow, crystalline tris(imido) complex [Li(THF)(4)][W(NAr3)Cl]
(2). Complex 2 is shown to be the kinetic product of this reaction sin
ce it reacts with byproduct H2NAr to afford W(NAr)(2)(NHAr)(2)(3). Exp
eriments are described that support the d(0) W(=NR)(2) functional grou
p in W(NAr)(2)Cl-2(THF)(2) (1) arising by an intramolecular alpha-H ab
straction in [W(NAr)(NHAr)(2)Cl-2(THF)(n)] (with loss of H2NAr), while
the formation of [W(NAr)(3)Cl](-)(2) from W(NAr)(2)Cl-2(THF)(2) (1) m
ost likely proceeds by an intermolecular deprotonation of nascent W(NA
r)(2)(NHAr)Cl by the second equivalent of [NHAr](-). These experiments
include synthesis and reactivity studies of W(NAr)(2)Cl-2(NH2Ar) (4),
W(NAr)(NEt(2))Cl-3(THF) (5), and W(NAr)(2)(NEt(2))Cl (6). The d(0) me
tal center in [W(NAr)(3)Cl](-)(2) is susceptible to nucleophilic attac
k as seen in its reactions with PMePh(2), PMe(3), [n-Bu(4)N]Br, MeLi,
and LiCH(2)SiMe(3) to afford the substitution products W(NAr)(3)(PMePh
(2)) (7), W(NAr)(3)(PMe(3)) (8), [n-Bu(4)N][W(NAr)(3)Br] (9), [Li(THF)
(4)] [W(NAr)(3)Me] (10), and [Li(THF)(4)][W(NAr)(3)(CH(2)SiMe(3))] (11
), respectively. Kinetic and mechanistic evidence is presented that su
ggests these reactions proceed by a bimolecular, S(N)2 attack at the d
(0) tungsten center. [Li(THF)(4)][W(NAr)(3)Cl] (2) crystallizes in the
monoclinic space group P2(1)/n (No. 14) with a = 13.787(4), Angstrom,
b = 17.348(5) Angstrom, c = 22.781(8) Angstrom, beta = 90.426(28)degr
ees, and V = 5448.5(30) Angstrom(3), with Z = 4 and D(calc) = 1.268 g
cm(-3). W(NAr)(3)(PMe(3)) (8) crystallizes in the orthorhombic space g
roup Pbca (No. 61) with a = 18.572(3) Angstrom, b = 25.966(4) Angstrom
, c = 16.819(3) Angstrom, and V = 8111(4) Angstrom(3), with Z = 8 and
D(calc) = 1.29 g cm(-3). The tungsten atom of [Li(THF)(4)][W(NAr)(3)Cl
] (2) is tetrahedrally coordinated with three virtually identical imid
o ligands with an average W-N bond length of 1.78 Angstrom and an aver
age W-N-C-ipso bond angle of 171 degrees. W(NAr)(3)(PMe(3)) (8) is als
o tetrahedrally coordinated and displays an average imido W-N bond len
gth of 1.79 Angstrom and slightly bent W-N-C-ipso bond angles (av 167
degrees), though one imido ligand is more strongly bent than the other
two. The electronic structure of the C-3v W(NAr)(3)L compounds sugges
ts a ligand-based, nonbonding a(2) HOMO comprised of a N(p pi) orbital
combination oriented perpendicular to the molecule's C-3 axis. Accord
ingly, an imido nitrogen is subject to electrophilic attack, as seen i
n the reactions of W(NAr)(3)(PMe(3)) (8) with HOAr'(Ar' = 2,6-C(6)H(3)
Me(2)), Me(3)SiI, MeI, and PhNCO that afford W(NAr)(2)(NHAr)(OAr') (12
), W(NAr)(2)[N(SiMe(3))Ar]I (13), W(NAr)(2)(NMeAr)I (14), and W[NArC(O
)NPh](NAr)(2)(PMe(3)) (15), respectively. Similarly, the reaction of [
Li(THF)(4)][W(NAr)(3)Me] (10) with [HNMe(3)]BPh(4) does not protonate
the W-Me bond but rather attacks the imido nitrogen to afford W(NAr)(2
)(NHAr)Me (16). W(NAr)(2)(NHAr)Me (16) does not eliminate CH4 upon the
rmolysis to afford base-free [W(NAr)(3)]; other attempts to. generate
this species are described.