Synthesis of Indium Amide Compounds.

Indium trichloride reacts with 3 equiv of lithium amide in diethyl ether to give In(NRR')(3) (R = Ph or t-Bu, R' = SiMe(3); R = t-Bu, R' = SiHMe(2)) and with 3 or 4 equiv of LiNMe(SiMe(3)) to yield Li[In{NMe(SiMe(3))}(4)]. The chloride also reacts with LiNPh(2) in THF to give the salt Li[In(NPh(2))(3)Cl] and with LiNRR' in pyridine to yield the neutral adduct In(NRR')(3)(py) (R = R' = Ph; R = Me, R' = SiMe(3)). The volatile liquids In[N(t-Bu)(SiHMe(2))](3) and In[NMe(SiMe(3))](3)(py) react with p-Me(2)Npy to form the solid compounds In[N(t-Bu)(SiHMe(2))](3)(p-Me(2)Npy) and In[NMe(SiMe(3))](3)(p-Me(2)Npy), respectively. X-ray crystallographic studies show that In(NPh(2))(3)(py), In[N(t-Bu)(SiHMe(2))](3)(p-Me(2)Npy), and the ether adduct of In[NPh(SiMe(3))](3) contain nearly planar In(amide)(3) fragments. Crystallographic studies also show that the anion in the salt [Li(THF)(4)][In(NPh(2))(3)Cl] is nearly tetrahedral and in [Li(p-Me(2)Npy)][In{NMe(SiMe(3))}(4)] the tetrahedral-like anion is bound to the Li cation via two amide nitrogens. The Li in the latter structure is also bonded to p-Me(2)Npy, resulting in a planar three-coordinate geometry for Li. Crystal data are the following. C(31)H(52)N(3)OSi(3)In at -50 degrees C: P2(1)/n (monoclinic), a = 11.003(2) Å, b = 18.678(3) Å, c = 17.618(3) Å, beta = 95.42(1) degrees, and Z = 4. C(41)H(35)N(4)In.C(7)H(8) at -50 degrees C: P&onemacr; (triclinic), a = 10.112(2) Å, b = 12.786(3) Å, c = 15.870(5) Å, alpha = 87.42(2) degrees, beta = 74.95(2) degrees, gamma = 78.15(2) degrees, and Z = 2. C(25)H(58)N(5)Si(3)In at -50 degrees C: P2(1)/c (monoclinic), a = 9.797(3) Å, b = 18.203(6) Å, c = 19.592(5) Å, beta = 100.27(2) degrees, and Z = 4. C(52)H(62)ClInLiN(3)O(4) at 23 degrees C: P2(1)/n (monoclinic), a = 16.076(2) Å, b = 17.185(2) Å, c = 18.447(3) Å, beta = 97.41(1) degrees, and Z = 4. C(23)H(58)InLiN(6)Si(4) at 23 degrees C: P&onemacr; (triclinic), a = 15.792(3) Å, b = 16.345(3) Å, c = 16.678(3) Å, alpha = 62.69(1) degrees, beta = 81.00(1) degrees, gamma = 86.94(1) degrees, and Z = 4.