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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >(Diphenylphosphino)alkylaldehyde affords hydride- or alkyl-[(diphenylphosphino)alkylacyl]rhodium(iii) or (diphenylphosphino)alkylester complexes: theoretical and experimental diastereoselectivity
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(Diphenylphosphino)alkylaldehyde affords hydride- or alkyl-[(diphenylphosphino)alkylacyl]rhodium(iii) or (diphenylphosphino)alkylester complexes: theoretical and experimental diastereoselectivity

机译：（二苯基膦基）烷基丙基提供氢化物或烷基 - [（二苯基膦酰基）烷基烷基铑（III）或（二苯基膦基）烷基酯络合物：理论和实验性的非对映选择性

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The reaction of [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) with racemic PPh2(CH(Ph)CH2CHO) and pyridine (py) led to the oxidative addition of the aldehyde, and a single geometric isomer of [RhHCl(PPh2(CH (Ph)CH2CO))(py)(2)] (1), with hydride trans to chloride, was obtained as a mixture of two diastereomers in a 95 : 5 ratio; this was in agreement with density functional theory (DFT) calculations. In a chloroform solution, the exchange of hydride by chloride yielded [RhCl2(PPh2(CH(Ph)CH2CO))(py)(2)] (2) as a mixture of a kinetically preferred species, trans-py-2a, and two diastereomers, cis-Cl-2b' and cis-Cl-2b, with cis pyridines and a chloride trans to acyl; as predicted by the DFT calculations, the latter was the major species. Complex 1 reacted with racemic PPh2(CH(Ph)CH2CHO) or PPh2(o-C6H4CHO) to afford [RhHCl(PPh2(CH(Ph)CH2CO))(kappa(1)-PPh2(CH(Ph)CH2CHO))(py)] (3) or [RhHCl(PPh2(o-C6H4CO))(kappa(1)-PPh2(CH(Ph)CH2CHO))(py)] (4), respectively, both with a dangling alkylaldehyde. Diastereomeric mixtures with the ratios 3a/3a' = 80 : 20 and 4a/4a' = 50 : 50 were obtained. Complex 4 reacted with N-donors to afford cationic [RhH (NN)(PPh2(o-C6H4CO))(kappa(1)-PPh2(CH(Ph)CH2CHO))]BPh4 (NN = 1,10-phenanthroline, 5; 2,2'-bipyridine, 6) or with 8-aminoquinoline (aqui) or 2-(aminomethyl) pyridine to yield imination products with terdentate ligands: [RhH(PPh2(o-C6H4CO))(kappa(3)-PNN)]BF4 (PNN = PPh2(CH(Ph)CH2CNC9H6N), 7 and PPh2(CH(Ph)CH2CNCH2C5H4N), 8, respectively. Compounds 5-8 were obtained as equimolar a/a' mixtures of diastereomers. Moreover, 5a and 5a' could be separated. [RhCl(NBD)] 2 reacted with racemic PPh2(CH(Ph)CH2CHO) and N-donors to provide nortricyclyl (Ntyl) derivatives [RhCl(NN)(Ntyl)(PPh2CH(Ph)CH2CO)] (NN = phen, 9 and bipy, 10) as an a/a' = 75 : 25 mixture of diastereomers. By reacting [RhCl(NBD)](2) with PPh2(CH(Ph)CH2CHO) and quinoline-8-carbaldehyde in methanol, the phosphino-ester complex [RhCl(Ntyl)(C9H6NCO)(.2-PPh2CH(Ph)CH2CO(OCH3)](11) was obtaine
机译：[rhCl（COD）]（2）（COD = 1,5-环辛二烯）与外消旋PPH2（CH（pH）CH 2 CH 2 COCHO）和吡啶（PY）的反应导致氧化醛和单个几何异构体在[rhHCl（PPH2（pH1）（CH（CH）（CH（CH）（CH）（CH（CH）（CH））（PY）（2）]（1）与氢化物反对氯化物中，得到2个非对映异构体的混合物，在95：5的比例中;这与密度泛函理论（DFT）计算一致。在氯仿溶液中，通过氯化物交换氢化物，得到[rhCl2（PPH2（pH）（pH）（pH）CH 2 CO））（py）（2）]（2）作为动力学上优选的物种，Trans-Py-2a和的混合物两种非对映异构体，CIS-CL-2B'和CIS-CL-2B，用CIS吡啶和氯化物转移到酰基;如DFT计算所预测的，后者是主要物种。复合物1与外消旋PPH2（CH（pH）CH 2 CH 2）或PPH2（O-C6H4CHO）反应，得到[RHHC1（PPH2（CH2（CH（pH）CH 2 CO））（Kappa（1）-PPH2（CH（pH）CH 2 CH 2 CH 2 CH 2））（ PY）]（3）或[RHHCL（PPH2（O-C6H4CO））（Kappa（1）-PPH2（CH2PH2（CH（pH）CH 2 CH 2 CH 2 CH 2 CH 2 CH 2））（PY）]（4）分别用悬空烷基醛。基于比率3a / 3a'= 80：20和4a / 4a'= 50：50的非对映异构体混合物。复合物4与N-供体反应以提供阳离子[rhH（NN）（PPH2（O-C6H4CO））（Kappa（1）-PPH2（CH（pH）CH 2 CH 2））] BPH4（NN = 1,10-菲啉，5 ; 2,2'-硼吡啶，6）或用8-氨基喹啉（Aqui）或2-（氨基甲基）吡啶，得到具有脱丁配体的化导形产物：[rhh（PPH2（O-C6H4CO））（Kappa（3）-PNN ）] BF4（PNN = PPH2（CH（pH）CH2CNC9H6N），7和PPH2（CH（pH）（CH）CH 2 CNCH 2 CC5H4N），8。将化合物5-8作为异映异构体的等摩尔A / A'混合物获得。此外，5A和5A'可以分离。[RhCl（NBD）] 2与外消旋PPH2（CH（pH）CH 2 CH 2 CH 2）和N-供体反应，以提供Nortricyclyl（NTYL）衍生物[RHCL（NN）（NTL）（PPH2CH（pH）CH 2 CO） [nn = phen，9和bipy，10）作为a / a'= 75：25的非对映异构体的混合物。通过使[rhCl（Nbd）]（2）与PPH2（CH（pH）CH 2 CH 2 CH 2）和喹啉-8反应-Carbaldehyde在甲醇中，磷酸氨酯复合物[RHCL（NTEL）（C9H6NCO）（2-PPH2CH（pH）CH 2 CO（OCH3）]（11）得到

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