عنوان

Phosphorus ligands derived from terpene alcohols as stereochemical probes

شماره

TLpq304306243

زبان متن نوشتاري يا گفتاري و مانند آن

انگلیسی

عنوان اصلي

Phosphorus ligands derived from terpene alcohols as stereochemical probes

نام عام مواد

[Thesis]

نام نخستين پديدآور

J. Wang

نام ساير پديدآوران

S. R. Stobart

نام ناشر، پخش کننده و غيره

University of Victoria (Canada)

تاریخ نشرو بخش و غیره

1996

نام خاص و کميت اثر

240

جزئيات پايان نامه و نوع درجه آن

Ph.D.

کسي که مدرک را اعطا کرده

University of Victoria (Canada)

امتياز متن

1996

متن يادداشت

A series of optically active tertiary phosphorus ligands, P(OR)nPh3-n (R = bornyl, menthyl, or isopinocamphyl; n = 1, 2, or 3, 1 - 9), containing chiral alkoxy groups derived from natural terpene alcohols, menthol, borneol, and isopinocampheol, are synthesized and characterized by various spectroscopic techniques. The reactions of these ligands with iron and cobalt carbonyl complexes are carried out, giving monomeric mono- and di-substituted iron(0) and dimeric di-substituted cobalt carbonyl complexes (Fe(CO)4L, Fe(CO)3L2, and (Co(CO)3L) 2, L = 1 - 9). The characterization of these complexes by IR and NMR spectrometries is discussed. Results of preliminary studies on hydroformylation reaction under oxo conditions catalysed by several cobalt complexes are presented. Pyrazolyl bridged di-iridium(I) systems, (Ir(CO)L(mu-pz)) 2 (L = P(OMen)Ph2, usd\underline{\rm 40},usd P(OBor)Ph2, usd\underline{\rm 41}usd, and P(OMen)2Ph, usd\underline{\rm 42}),usd are prepared as diastereomers with unequal thermodynamic distribution. The X-ray crystal structure of usd\underline{\rm 41}usd shows cocrystallization of the two diastereomers in the same unit cell, which provides 1:1 kinetic distribution of the two isomers. Kinetic studies of the interconversion from the kinetic ratio to the thermodynamic ratio of the two diastereomers in usd\underline{\rm 41}usd indicates the existence of a slow inversion process of the six-membered central metallocycle in usd\underline{\rm 41}.usd Oxidative addition of MeI to usd\underline{\rm 41}usd generates a pair of diastereomeric adducts (usd\underline{\rm 43})usd in kinetic distribution, which is slowly converted to its thermodynamic distribution, implying a very slow reductive elimination of MeI. Oxidative additions of exo- and endo-norbornyl iodide to (Ir(CO)2(\mu-pz)) 2 results in same product (usd\underline{\rm 44}).usd Possible mechanisms for this process are discussed. Bisdiphenylphosphinoalkcylsilane containing chiral menthoxy group ((o-PPh2C6H4CH2)\sb2(MenO)SiH, usd\underline{\rm 47})usd is prepared and characterized. Its four-coordinate square planar platinum complex (Pt (Si(o-PPh2C6H4CH2)\sb2(OMen)) Cl, usd\underline{\rm 48})usd and five-coordinate iridium(I) complex (IrH (Si(o-PPh2C6H4CH2)\sb2(OMen)) Cl, usd\underline{\rm 49})usd are synthesized. Isomerizations of usd\underline{\rm 49}usd and its CO adducts, Ir (Si(MenO)(CH2C6H4PPh2)\sb2\rbrack(CO)HCl (usd\underline{\rm 55}usd and usd\underline{\rm 56}),usd are studied in relation to their methyl analogues.

موضوع مستند نشده

Analytical chemistry

موضوع مستند نشده

Chemistry

موضوع مستند نشده

Chemistry

موضوع مستند نشده

Pure sciences

مستند نام اشخاص تاييد نشده

J. Wang

مستند نام اشخاص تاييد نشده

S. R. Stobart

نام الکترونيکي

فرمت انتشار

p

نوع ماده

[Thesis]

کد کاربرگه

276903

سطح دسترسي

a

تكميل شده

Y