SYNTHESIS OF INDIUM AMIDE COMPOUNDS

Indium trichloride reacts with 3 equiv of lithium amide in diethyl eth er to give In(NRR')(3) (R = Ph or t-Bu, R' = SiMe3; R = t-Bu, R' = SiH Me2) and with 3 or 4 equiv of LiNMe(SiMe3) to yield Li[In{NMe(SiMe3)}( 4)]. The chloride also reacts with LiNPh2 in THF to give the salt Li[I n(NPh2)(3)CI] and with LiNRR' in pyridine to yield the neutral adduct In(NRR')(3)(py) (R = R'= Ph; R = Me, R' = SiMe3): The volatile liquids In[N(t-Bu)(SiHMe2)](3) and In[NMe(SiMe3)](3)(py) react with p-Me(2)Np y to form the, solid compounds In[N(t-Bu)(SiHMe2)](3)(p-Me(2)Npy) and In[NMe(SiMe3)](3)(p-Me(2)Npy), respectively. X-ray crystallographic st udies show that In(NPh2)(3)(py), In[N(t-Bu)(SiHMe2)](3) (p-Me(2)Npy), and the ether adduct of In[NPh(SiMe3)](3) contain nearly planar In(ami de)(3) fragments; Crystallographic studies also show that the anion in the salt [Li(THF)(4)][In(NPh2)(3)Cl] is nearly tetrahedral and in [Li (p-M(2)Npy)] [In(NMe(SiMe3)}(4)] the tetrahedral-like anion is bound t o the Li cation via two amide nitrogens. The Li in the latter structur e is also bonded to p-Me(2)Npy, resulting in a planar three-coordinate geometry for Li. Crystal data are the following. C31H52N3OSi3In at -5 0 degrees C P2(1)/n (monoclinic), a =11.003(2) Angstrom, b = 18.678(3) Angstrom, c = 17.618(3) Angstrom, beta = 95.42(1)degrees, and Z = 4. C41H35N4In . C7H8 at -50 degrees C: P (1) over bar (triclinic), a = 10 .112(2) Angstrom, b = 12.786(3) Angstrom, c = 15.870(5) Angstrom, alph a = 87.42(2)degrees, beta = 74.95(2)degrees, gamma = 78.15(2)degrees, and Z = 2. C25H58N5Si3In at -50 degrees C: P2(1)/c (monoclinic), a = 9 .797(3) Angstrom, b = 18.203(6) Angstrom, c = 19.592(5) Angstrom, beta = 100.27(2)degrees, and Z = 4. C52H62ClInLiN3O4 at 23 degrees C: P2(1 )/n (monoclinic), a = 16.076(2) Angstrom, b = 17.185(2) Angstrom, c = 18.447(3) Angstrom, beta = 97.41(1)degrees, and Z = 4. C23H58InLiN6Si4 at 23 degrees C: P (1) over bar (triclinic) a = 15.792(3) Angstrom, b = 16.345(3) Angstrom, c = 16.678(3) Angstrom, alpha = 62.69(1)degrees , beta = 81.00(1)degrees, gamma = 86.94(1)degrees, and Z = 4.