Kim Jungsook, Bott Simon G., Hoffman David M.
Department of Chemistry, University of Houston, Houston, Texas 77204.
Inorg Chem. 1998 Jul 27;37(15):3835-3841. doi: 10.1021/ic971138u.
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 InN(t-Bu)(SiHMe(2)) and InNMe(SiMe(3))(py) react with p-Me(2)Npy to form the solid compounds InN(t-Bu)(SiHMe(2))(p-Me(2)Npy) and InNMe(SiMe(3))(p-Me(2)Npy), respectively. X-ray crystallographic studies show that In(NPh(2))(3)(py), InN(t-Bu)(SiHMe(2))(p-Me(2)Npy), and the ether adduct of InNPh(SiMe(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.
三氯化铟在乙醚中与3当量的酰胺锂反应，生成In(NRR')(3)（R = 苯基或叔丁基，R' = 三甲基硅基；R = 叔丁基，R' = 甲基二硅基氢），与3或4当量的LiNMe(SiMe(3))反应生成Li[In{NMe(SiMe(3))}(4)]。该氯化物还在四氢呋喃中与LiNPh(2)反应生成盐Li[In(NPh(2))(3)Cl]，在吡啶中与LiNRR'反应生成中性加合物In(NRR')(3)(py)（R = R' = 苯基；R = 甲基，R' = 三甲基硅基）。挥发性液体InN(t-Bu)(SiHMe(2))和InNMe(SiMe(3))(py)分别与对二甲氨基吡啶反应，形成固体化合物InN(t-Bu)(SiHMe(2))(p-Me(2)Npy)和InNMe(SiMe(3))(p-Me(2)Npy)。X射线晶体学研究表明，In(NPh(2))(3)(py)、InN(t-Bu)(SiHMe(2))(p-Me(2)Npy)以及InNPh(SiMe(3))的乙醚加合物含有近乎平面的In(酰胺)(3)片段。晶体学研究还表明，盐[Li(THF)(4)][In(NPh(2))(3)Cl]中的阴离子近乎四面体，在[Li(p-Me(2)Npy)][In{NMe(SiMe(3))}(4)]中，类似四面体的阴离子通过两个酰胺氮与锂阳离子相连。后一种结构中的锂也与对二甲氨基吡啶键合，使得锂具有平面三配位几何结构。晶体数据如下。C(31)H(52)N(3)OSi(3)In，在-50℃时：P2(1)/n（单斜晶系），a = 11.003(2) Å，b = 18.678(3) Å，c = 17.618(3) Å，β = 95.42(1)°，Z = 4。C(41)H(35)N(4)In.C(7)H(8)，在-50℃时：P&onemacr;（三斜晶系），a = 10.112(2) Å，b = 12.786(3) Å，c = 15.870(5) Å，α = 87.42(2)°，β = 74.95(2)°，γ = 78.15(2)°，Z = 2。C(25)H(58)N(5)Si(3)In，在-
