Mosquera Marta E G, Ruiz Javier, García Gabriel, Marquínez Fernando
Departamento de Química Inorgánica Facultad de Farmacia, Universidad de Alcalá 28871 Alcala de Henares, Madrid, Spain.
Chemistry. 2006 Oct 10;12(29):7706-16. doi: 10.1002/chem.200600367.
The diphosphinoketenimine ligand in the neutral complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C=NR}] (1 a: R = Ph; 1 b: R = p-tolyl) undergoes nucleophilic attack by MeLi and nBuMgCl yielding, after hydrolysis, the diphosphinoenamine-containing complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C(R')NHR}] (3 a,b: R' = Me; 4 a,b: R' = nBu). Complex 1 a reacts under the same conditions with H(2)C=C=CHMgBr to afford fac-[MnI(CO)(3){(PPh(2))(2)C=C(CH(2)CC[triple chemical bond]CH)NHR}] (5 a), which contains a terminal alkyne group on the alpha-carbon atom of the diphosphinoenamine ligand. The cationic complexes fac-Mn(CO)(4){(PPh(2))(2)C=C=NR} (6) react with H(2)C=C=CHMgBr to afford diphosphinomethanide derivatives bearing three different types of functional groups, depending upon the substituent on the nitrogen atom of the ketenimine: cumulene in fac-[Mn(CO)(4){(PPh(2))(2)C--C(CH=C=CH(2))=N-xylyl}] (7 d), internal alkyne in fac-[Mn(CO)(4){(PPh(2))(2)C--C(C[triple chemical bond]CCH(3))=NtBu}] (8), and quinoline in 9 (R = Ph), whose formation implies an unusual cyclization process. Protonation of 7 d, 8, and 9 with HBF(4) occurs at the nitrogen atom to give the cationic derivatives 10 d, 11, and 12, respectively, which contain the corresponding functionalized diphosphine ligands. Irradiation of 3 a,b and 4 a,b with Vis/UV light makes it possible to isolate the free ligands (PPh(2))(2)C=C(R')NHR (13 a,b and 14 a,b), completing the metal-assisted synthesis of these novel functionalized diphosphines. Irradiation of 12 with Vis/UV light generates free phosphinoquinoline ligand 15, which readily affords a complex 16 containing 15 as a P,N-chelating ligand when treated with [PdCl(2)(NCMe)(2)], thus demonstrating its coordination capability.
中性配合物fac-[MnI(CO)₃{(PPh₂)₂C=C=NR}]（1a：R = Ph；1b：R = 对甲苯基）中的二膦基乙酮亚胺配体受到MeLi和nBuMgCl的亲核进攻，水解后生成含二膦基烯胺的配合物fac-[MnI(CO)₃{(PPh₂)₂C=C(R')NHR}]（3a,b：R' = Me；4a,b：R' = nBu）。配合物1a在相同条件下与H₂C=C=CHMgBr反应，得到fac-[MnI(CO)₃{(PPh₂)₂C=C(CH₂CC≡CH)NHR}]（5a），其在二膦基烯胺配体的α碳原子上含有一个末端炔基。阳离子配合物fac-[Mn(CO)₄{(PPh₂)₂C=C=NR}]⁺（6）与H₂C=C=CHMgBr反应，根据乙酮亚胺氮原子上的取代基不同，得到带有三种不同类型官能团的二膦基甲烷衍生物：fac-[Mn(CO)₄{(PPh₂)₂C--C(CH=C=CH₂)=N-二甲苯基}]（7d）中的累积烯、fac-[Mn(CO)₄{(PPh₂)₂C--C(C≡CCH₃)=NtBu}]（8）中的内炔以及9（R = Ph）中的喹啉，其形成意味着一个不寻常的环化过程。用HBF₄对7d、8和9进行质子化反应，分别在氮原子上发生，得到阳离子衍生物10d、11和12，它们含有相应的官能化二膦配体。用可见光/紫外光照射3a,b和4a,b，可以分离出游离配体(PPh₂)₂C=C(R')NHR（13a,b和14a,b），从而完成了这些新型官能化二膦的金属辅助合成。用可见光/紫外光照射12生成游离膦基喹啉配体15，当用[PdCl₂(NCMe)₂]处理时，15很容易得到一个以15为P,N-螯合配体的配合物16，从而证明了其配位能力。
