ORTHOMANGANATED ARENES IN SYNTHESIS .9. PHOTOCHEMICAL-REACTIONS OF ALKYNES WITH ORTHOMANGANATED TRIPHENYL PHOSPHITE
ORTHOMANGANATED ARENES IN SYNTHESIS .9. PHOTOCHEMICAL-REACTIONS OF ALKYNES WITH ORTHOMANGANATED TRIPHENYL PHOSPHITE
复制标题
DOI：
10.1021/om00026a026
复制
发表时间：
1993-02-01
期刊：
影响因子：
2.8
通讯作者：
NICHOLSON, BK
中科院分区：
文献类型：
--
作者：
GRIGSBY, WJ;MAIN, L;NICHOLSON, BK
在紫外光照射下，三硫化锰基亚磷酸三苯酯（PHO）_2P（OC_6H_4）Mn（CO）_4（1）与炔（C_2Ph_2，C_2（COOME）_2，PhCCH，Me_3SiCCH）反应，生成炔插入MN-C键的产物。 主要产物是七元金属环物种（PHO）2 P（OC 6 H4）C（R2）=C（R1）Mn（CO）4（2）（两种不对称炔的区域异构体）。 由C2 Ph 2反应还获得通过插入C2 Ph 2和CO两者形成的（PHO）2 POC 6 H4）C（Ph）=C（Ph）C（O）Mn（CO）3（4），以及化合物{2，6-[PhCH=C（Ph）] 2C 6 H3 O}{2-[PhCH=C（Ph）] C6 H4 O} POC 6 H4）Mn（CO）4（3），其通过用-C（Ph）=C（Ph）取代而从1衍生H基团在三个邻位网站上的非金属苯氧基环的插入/脱金属步骤的序列。 从与PhCCH的反应中还分离出金属乙炔化物PhCCMn（CO）3[P（OPh）3]2（6）。 晶体结构描述为2 e（R1 = Ph，R2 = H;三斜晶系，空间群P1 BAR，a = 10.619（11）埃，B = 10.896（6）埃，c = 11.619（8）埃，α = 77.68，β = 80.81（7）度，γ = 80.31（6）度，Z = 2，2772次反射，R = 0.039），3（单斜晶系，空间群P2（1）/n，a = 10.743（6）埃，B = 27.456（23）埃，c = 17.536（14）埃，β = 104.86（5）度，Z = 4，3941次反射，R = 0.0599），4（单斜晶系，空间群P2（1）/n，a = 9.907（6）埃，B = 18.458（11）埃，c = 16.539（8）埃，β = 94.35（4）度，Z = 4，2565次反射，R = 0.104），和6（斜方晶系，空间群P2（1）2（1）2（1），a = 19.888（6）埃，B = 19.732（8）埃，c = 10.467（4）埃，Z = 4，3085次反射，R = 0.0523）。
The reaction of othomanganated triphenyl phosphite, (PHO)2P(OC6H4)Mn(CO)4 (1) with alkynes (C2Ph2, C2(COOME)2, PhCCH, Me3SiCCH) under UV irradiation gives products derived from insertion of the alkyne into the MN-C bond. The main products are the seven-membered metallacyclic species (PHO)2P(OC6H4)C(R2)=C(R1)Mn(CO)4 (2) (both regioisomers for the unsymmetrical alkynes). Also obtained from the C2Ph2 reaction was (PHO)2POC6H4)C(Ph)=C(Ph)C(O)Mn(CO)3 (4) formed by insertion of both C2Ph2 and CO, and a compound {2,6-[PhCH=C(Ph)]2C6H3O}{2-[PhCH=C(Ph)]C6H4O}POC6H4)Mn(CO)4 (3) derived from 1 by substitution with -C(Ph)=C(Ph)H groups at three of the ortho sites on the unmetalated phenoxy rings by a sequence of insertion/demetalation steps. A metal acetylide, PhCCMn(CO)3[P(OPh)3]2 (6) was also isolated from the reaction with PhCCH. Crystal structures are described for 2e (R1 = Ph, R2 = H; triclinic, space group P1BAR, a = 10.619 (11) angstrom, b = 10.896 (6) angstrom, c = 11.619 (8) angstrom, alpha = 77.68, beta = 80.81 (7)-degrees, gamma = 80.31 (6)-degrees, Z = 2, 2772 reflections, R = 0.039), 3 (monoclinic, space group P2(1)/n, a = 10.743 (6) angstrom, b = 27.456 (23) angstrom, c = 17.536 (14) angstrom, beta = 104.86 (5)-degrees, Z = 4, 3941 reflections, R = 0.0599), 4 (monoclinic, space group P2(1)/n, a = 9.907 (6) angstrom, b = 18.458 (11) angstrom, c = 16.539 (8) angstrom, beta = 94.35 (4)-degrees, Z = 4, 2565 reflections, R = 0.104), and 6 (orthorhombic, space group P2(1)2(1)2(1), a = 19.888 (6) angstrom, b = 19.732 (8) angstrom, c = 10.467 (4) angstrom, Z = 4, 3085 reflections, R = 0.0523).