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首页> 外文期刊>Journal of Molecular Spectroscopy >Microwave spectra, ab initio and DFT calculations and molecular structure for (η~7-cycloheptatriene)Ti(η5-cyclopentadienyl) and (η~7-cycloheptatriene)Cr(η~5-cyclopentadienyl)
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Microwave spectra, ab initio and DFT calculations and molecular structure for (η~7-cycloheptatriene)Ti(η5-cyclopentadienyl) and (η~7-cycloheptatriene)Cr(η~5-cyclopentadienyl)

机译：（η〜7-环庚三烯）Ti（η5-环戊二烯基）和（η〜7-环庚三烯）Cr（η〜5-环戊二烯基）的微波光谱，从头算和DFT计算以及分子结构

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Microwave spectra of 1-d-(η~7-cycloheptatriene) 48Ti(η~5-cyclopentadienyl) (CHT-Ti-Cp) and two singly substituted 13C isotopomers were measured and gas phase structural parameters were determined. Rotational transitions were also measured for (η~7-cycloheptatriene)52Cr(η5- cyclopentadienyl). Rotational constants for the Ti complex were found to be A = 1720(4) MHz, B = 769.269(1) MHz and C = 766.131(1) MHz and for [ ~(13)CC_6H_7-~(48)Ti-C_5H _5], A = 1773(2) MHz, B = 769.6931(4) MHz and C = 761.1789(5) MHz and for [1-d-C_7H_6~(48)TiC_5H_5] and A = 1270(5) MHz, B = 767.0142(9) MHz and C = 765.323(1) MHz for [C _7H_7~(48)Ti~(13)CC_4H _5]. A structural analysis for the (CHT-Ti-Cp) data showed that the cycloheptatriene ring protons droop towards titanium as predicted by DFT and MP2 calculations. The droop of the protons toward the metal was experimentally determined to be 8.0(2)°out of the plane of the cycloheptatriene ring. The ring center distance to titanium was found to be 2.01(3) for Ti-Cp and 1.48(3) for Ti-CHT using a least squares fit to the measured rotational constants and fixing many of the structural parameters to the calculated values. The spectrum of the normal isotopomer (η~7-cycloheptatriene) Ti(η~5-cyclopentadienyl) was re-measured and a discussion of the possible ~(47)Ti quadrupole coupling constants is presented. The chromium analog K = 0 spectrum was analyzed to obtain B = 851.229 MHz, and DJ = 0.028(6) kHz. Results from structure calculations are reported and discussed for (CHT-M-Cp) complexes with M = Ti, Cr, Zr, Hf, Mo, W using MP2, B3PW91 and B3LYP methods.
机译：测量了1-d-（η〜7-环庚三烯）48Ti（η〜5-环戊二烯基）（CHT-Ti-Cp）和两个单取代的13C异构体的微波光谱，并确定了气相结构参数。还测量了（η〜7-环庚三烯）52Cr（η5-环戊二烯基）的旋转跃迁。 Ti复合物的旋转常数为A = 1720（4）MHz，B = 769.269（1）MHz和C = 766.131（1）MHz，[〜（13）CC_6H_7-〜（48）Ti-C_5H _5 ]，对于[1-d-C_7H_6〜（48）TiC_5H_5]，A = 1773（2）MHz，B = 769.6931（4）MHz和C = 761.1789（5）MHz，A = 1270（5）MHz，B =对于[C _7H_7〜（48）Ti〜（13）CC_4H _5]，为767.0142（9）MHz，C = 765.323（1）MHz。对（CHT-Ti-Cp）数据的结构分析表明，正如DFT和MP2计算所预测的那样，环庚三烯环质子向钛下垂。通过实验确定质子向金属的下垂是在环庚三烯环平面之外的8.0（2）°。发现钛的环中心距离对于Ti-Cp为2.01（3），对于Ti-CHT为1.48（3），这是通过最小二乘法拟合所测得的旋转常数并将许多结构参数固定为计算值。重新测量了正常同位素（η〜7-环庚三烯）Ti（η〜5-环戊二烯基）的光谱，并讨论了可能的〜（47）Ti四极偶合常数。分析铬类似物K = 0的频谱，以获得B = 851.229 MHz，DJ = 0.028（6）kHz。报告并讨论了使用MP2，B3PW91和B3LYP方法对M = Ti，Cr，Zr，Hf，Mo，W的（CHT-M-Cp）配合物的结构计算结果。

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