含双（恶唑啉 - 2'-基）吡啶配体的钌（II）配合物的立体化学控制合成。反式 - [RuCl₂(PPh₃){κ³ - N,N,N-(S,S)-(i)Pr - pybox}]和[RuCl(=C=C=CPh₂)(PPh₃){κ³ - N,N,N-(S,S)-(i)Pr - pybox}][PF₆]的X射线晶体结构（(S,S)-(i)Pr - pybox = 2,6 - 双[4'-(S)-异丙基恶唑啉 - 2'-基]吡啶）。

Stereochemically Controlled Synthesis of Ruthenium(II) Complexes Containing Bis(oxazolin-2'-yl)pyridine Ligands. X-ray Crystal Structures of trans-[RuCl(2)(PPh(3)){kappa(3)-N,N,N-(S,S)-(i)Pr-pybox}] and [RuCl(=C=C=CPh(2))(PPh(3)){kappa(3)-N,N,N-(S,S)-(i)Pr-pybox}][PF(6)] ((S,S)-(i)Pr-pybox= 2,6-Bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine).

作者信息

Cadierno Victorio, Gamasa M. Pilar, Gimeno José, Iglesias Luis, García-Granda Santiago

机构信息

Departamento de Química Física y Analítica, Universidad de Oviedo, E-33071 Oviedo, Spain.

出版信息

Inorg Chem. 1999 Jun 14;38(12):2874-2879. doi: 10.1021/ic9813258.

DOI:10.1021/ic9813258

PMID:11671033

Abstract

The treatment of achiral and chiral bis(oxazolin-2'-yl)pyridine (pybox) complexes trans-[RuCl(2)(eta(2)-H(2)C=CH(2))(k(3)-N,N,N-pybox)] [pybox= 2,6-bis(dihydrooxazolin-2'-yl)pyridine] (1a) and [RuCl(2)(eta(2)-H(2)C=CH(2))(k(3)-N,N,N-(SS)-(i)Pr-pybox}] [(SS)-(i)Pr-pybox= 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine] (1b) with an excess of triphenylphosphine in dichloromethane at 50 degrees C leads to the formation of the first ruthenium(II) derivatives containing both bis(oxazolin-2'-yl)pyridine and phosphine ligands trans-[RuCl(2)(PPh(3))(kappa(3)-N,N,N-pybox)] (2a) and trans-[RuCl(2)(PPh(3)){kappa(3)-N,N,N-(SS)-(i)Pr-pybox}] (2b). Chiral complex 2b slowly isomerizes in acetone at 50 degrees C to generate cis-[RuCl(2)(PPh(3)){kappa(3)-N,N,N-(SS)-(i)Pr-pybox}] (3). Complex 3 can be also obtained from the reaction of 1b with PPh(3) in MeOH. The structure of 3 has been confirmed by X-ray crystallography [orthorhombic; space group P2(1)2(1)2(1); Z = 4; a = 12.772(6) Å, b = 15.208(5) Å, c = 19.601(7) Å; final R1= 0.0565 and wR2 = 0.0944 (both for I > 2sigma(I))]. The reaction of the achiral pybox complex 2a with 1,1-diphenyl-2-propyn-1-ol and AgBF(4) in CH(2)Cl(2) stereoselectively affords the cationic allenylidene derivative [RuCl(=C=C=CPh(2))(PPh(3))(kappa(3)-N,N,N-pybox)][BF(4)] (4a), while the methoxycarbene complex [RuCl{=C(OMe)CH=CPh(2)}(PPh(3))(kappa(3)-N,N,N-pybox)][PF(6)] (5) is obtained when the reaction is conducted in methanol and in the presence of NaPF(6), via the addition of MeOH to the initially formed allenylidene complex 4a. In contrast, the chiral pybox complex 2b reacts with 1,1-diphenyl-2-propyn-1-ol and NaPF(6) in MeOH to give the stable allenylidene complex [RuCl(=C=C=CPh(2))(PPh(3)){kappa(3)-N,N,N-(SS)-(i)Pr-pybox}][PF(6)] (4b). The X-ray crystal structure of 4b [orthorhombic; space group P2(1)2(1)2(1); Z = 4; a = 14.79(3) Å, b = 16.254(8) Å, c = 22.917(18) Å; final R1 = 0.0545 and wR2 = 0.1381 (both for I > 2sigma(I))] shows an octahedral coordination of the ligands around the ruthenium atom with the chloride and triphenylphosphine ligands in a trans arrangement and mutually cis with respect to the allenylidene moiety. The allenylidene complex 4b is also formed by the reaction of the cis dichloride complex 3 with 1,1-diphenyl-2-propyn-1-ol and NaPF(6) in MeOH. IR, (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR data of all novel compounds are also reported.

摘要

在手性和非手性双（恶唑啉 - 2'-基）吡啶（pybox）配合物反式 - [RuCl₂(η² - H₂C = CH₂)(κ³ - N,N,N - pybox)] [pybox = 2,6 - 双（二氢恶唑啉 - 2'-基）吡啶]（1a）和[RuCl₂(η² - H₂C = CH₂)(κ³ - N,N,N - (SS)-(i)Pr - pybox)] [(SS)-(i)Pr - pybox = 2,6 - 双[4' - (S)-异丙基恶唑啉 - 2'-基]吡啶]（1b）于50℃在二氯甲烷中与过量三苯基膦反应，导致形成了首批同时含有双（恶唑啉 - 2'-基）吡啶和膦配体的钌（II）衍生物反式 - [RuCl₂(PPh₃)(κ³ - N,N,N - pybox)]（2a）和反式 - [RuCl₂(PPh₃){κ³ - N,N,N - (SS)-(i)Pr - pybox}]（2b）。手性配合物2b在50℃于丙酮中缓慢异构化生成顺式 - [RuCl₂(PPh₃){κ³ - N,N,N - (SS)-(i)Pr - pybox}]（3）。配合物3也可由1b与PPh₃在甲醇中反应得到。3的结构已通过X射线晶体学确定[正交晶系；空间群P2(1)2(1)2(1)；Z = 4；a = 12.772(6) Å，b = 15.208(5) Å，c = 19.601(7) Å；最终R1 = 0.0565，wR2 = 0.0944（两者均针对I > 2σ(I)）]。非手性pybox配合物2a与1,1 - 二苯基 - 2 - 丙炔 - 1 - 醇以及AgBF₄在CH₂Cl₂中反应立体选择性地得到阳离子亚丙二烯基衍生物[RuCl(=C = C = CPh₂)(PPh₃)(κ³ - N,N,N - pybox)][BF₄]（4a），而当反应在甲醇中且在NaPF₆存在下进行时，通过向最初形成的亚丙二烯基配合物4a中加入甲醇得到甲氧基卡宾配合物[RuCl{=C(OMe)CH = CPh₂}(PPh₃)(κ³ - N,N,N - pybox)][PF₆]（5）。相反，手性pybox配合物2b与1,1 - 二苯基 - 2 - 丙炔 - 1 - 醇以及NaPF₆在甲醇中反应得到稳定的亚丙二烯基配合物[RuCl(=C = C = CPh₂)(PPh₃){κ³ - N,N,N - (SS)-(i)Pr - pybox}][PF₆]（4b）。4b的X射线晶体结构[正交晶系；空间群P2(1)2(1)2(1)；Z = 4；a = 14.79(3) Å，b = 16.254(8) Å，c = 22.917(18) Å；最终R1 = 0.0545，wR2 = 0.1381（两者均针对I > 2σ(I)）]显示配体围绕钌原子呈八面体配位，氯和三苯基膦配体呈反式排列且相对于亚丙二烯基部分相互呈顺式。亚丙二烯基配合物4b也可由顺式二氯配合物3与1,1 - 二苯基 - 2 - 丙炔 - 1 - 醇以及NaPF₆在甲醇中反应形成。还报道了所有新化合物的红外光谱、¹H、³¹P{(¹H)}和¹³C{(¹H)}核磁共振数据。