CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
Dalton Trans. 2012 Sep 14;41(34):10453-64. doi: 10.1039/c2dt30886j. Epub 2012 Jul 20.
Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph(2)PNHR (R = p-MeC(6)H(4), Bu(t)) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph(2))=N(8-C(9)H(6)N) (1a, R = p-MeC(6)H(4); 1b, R = Bu(t). C(9)H(6)N = quinolyl)). Reaction of 1a with (DME)NiCl(2) generates a nickel complex [NiCl(2){N(8-C(9)H(6)N)=P(Ph(2))NH(p-MeC(6)H(4))}] (2a). Treatment of 1b with (DME)NiCl(2) and following with NaH produces [NiCl{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl(2) with [Li{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N) (6, Py = pyridyl) and PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N) (8), respectively, with (DME)NiCl(2) yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl(2){2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (7) and [NiCl(2){PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (9). Similar reaction between Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N) (10) and (DME)NiCl(2) results in five-coordinate N,N,P-chelate nickel complex [NiCl(2){Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (11). Treatment of (8-C(9)H(6)N)N=P(Ph(2))CH(2) (12) [prepared from (Ph(2)P)(2)CH(2) and 2 equiv. of 8-azidoquinoline] with LiBu(n) and (DME)NiCl(2) successively affords [NiCl{(8-C(9)H(6)N)NP(Ph(2))}(2)CH] (13). The new compounds were characterized by (1)H, (13)C and (31)P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.
合成并表征了含喹啉基配体的锂和镍配合物。8-叠氮喹啉与 Ph(2)PNHR（R = p-MeC(6)H(4)，Bu(t)）反应生成 N-(8-喹啉基)亚膦酰胺 RNHP(Ph(2))=N(8-C(9)H(6)N)（1a，R = p-MeC(6)H(4)；1b，R = Bu(t). C(9)H(6)N = 喹啉基））。1a 与(DME)NiCl(2)反应生成镍配合物[NiCl(2){N(8-C(9)H(6)N)=P(Ph(2))NH(p-MeC(6)H(4))}]（2a）。1b 与(DME)NiCl(2)和随后的 NaH 反应生成[NiCl{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}]（4）。通过(DME)NiCl(2)与[Li{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}]（5）反应也得到了 4，5 是通过 1b 的锂化反应制备的。2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N)（6，Py = 吡啶基）和 PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N)（8）分别与(DME)NiCl(2)反应得到两个五配位 N,N,N-螯合镍配合物，[NiCl(2){2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N)}]（7）和[NiCl(2){PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N)}]（9）。Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N)（10）与(DME)NiCl(2)的类似反应得到五配位 N,N,P-螯合镍配合物[NiCl(2){Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N)}]（11）。(8-C(9)H(6)N)N=P(Ph(2))CH(2)（12）[由(Ph(2)P)(2)CH(2)和 2 当量的 8-叠氮喹啉制备]与 LiBu(n)和(DME)NiCl(2)依次反应得到[NiCl{(8-C(9)H(6)N)NP(Ph(2))}(2)CH]（13）。新化合物通过（1）H、（13）C 和（31）P NMR 光谱（对于非顺磁性化合物）、IR 光谱（对于镍配合物）和元素分析进行了表征。配合物 2a、4、7、9、11 和 13 还通过单晶 X 射线衍射技术进行了表征。评估了这些镍配合物在芳基锌试剂与芳基氯和芳基三甲基铵盐的交叉偶联反应中的催化性能。在催化芳基锌试剂与芳基氯或芳基三甲基溴化物的反应中，配合物 7 的活性最高。
