铟酰胺化合物的合成

Synthesis of Indium Amide Compounds.

作者信息

Kim Jungsook, Bott Simon G., Hoffman David M.

机构信息

Department of Chemistry, University of Houston, Houston, Texas 77204.

出版信息

Inorg Chem. 1998 Jul 27;37(15):3835-3841. doi: 10.1021/ic971138u.

DOI:10.1021/ic971138u

PMID:11670487

Abstract

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.

摘要

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-