کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1409332 1501751 2014 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Conformation analysis of triphenylphosphine in trans and cis triphenylphosphine-substituted Fischer carbene complexes
ترجمه فارسی عنوان
تجزیه و تحلیل سازگاری ترفنیل فسفین در پروتئین فسفری کربن مجتمع ترانس و سینسفورفیلفسفین
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آلی
چکیده انگلیسی


• Synthesis of novel [(CO)4(PPh3)M(OEt)(aryl)-carbene] complexes, M = Cr or Mo.
• First crystal structure of a trans-[(CO)4(PPh3)M-carbene], M = W.
• Crystal structures of cis-[(CO)4(PPh3)M-carbene] complexes.
• PPh3 orientation in octahedral trans- and cis-[(CO)4(PPh3)M-carbene] complexes.
• Remarkable performance of DFT to determine PPh3 orientation.

The synthesis and selected crystal structures of novel (M = Cr or Mo) and known (M = W) [(CO)4(PPh3)M = C(OEt)R] complexes, M = Cr, R = 2-thienyl (1), 2-furyl (2); M = Mo, R = 2-thienyl (3), 2-furyl (4); M = W, R = 2-thienyl (5), 2-furyl (6), are presented. Experimental crystal structures and DFT calculations of selected trans- and cis-triphenylphosphine-substituted Fischer carbene complexes, illustrate that the minimum energy conformation of triphenylphosphine (PPh3) in octahedral [(CO)4(PPh3)ML]-complexes generally have distinct features that can be described in terms of the “plane of nadir energy”, a plane linking all points of minimum steric compression between the ligands. The generally observed orientation of PPh3 involves a correlated feathering of the phenyl groups with the PCipso bond of one phenyl group orientated near parallel to the nadir plane, and a meta carbon (Cm) of the other two phenyl groups orientated as near as possible to the nadir plane, orthogonal to the first. Although the orientation of PPh3 in 6-trans, [(CO)4(PPh3)W = C(OEt)2-furyl], deviates from this, DFT correctly calculated the unexpected and not generally observed PPh3 orientation.

Orientation of triphenylphosphine in octahedral [(CO)4(PPh3)W-carbene] complexes.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure - Volumes 1065–1066, 22 May 2014, Pages 29–38
نویسندگان
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