Static and ab initio molecular dynamics study of the titanium(IV)-constrained geometry catalyst (CpSiH2NH)Ti-R+. 2. Chain termination and long chain branching

Organometallics

Volumn 16, Issue 15, 1997, Pages 3454-3468

  Woo, Tom K ^a   Margl, Peter M ^a   Ziegler, Tom ^a   Blöchl, Peter E ^b  

^a UNIVERSITY OF CALGARY   (Canada)

^b IBM RESEARCH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001251327     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970126d     Document Type: Article

References (72)

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38. A similar process is shown in Scheme 3b with respect to the β-hydrogen transfer to the metal.
39. Hysteresis refers to the difference in sampling between forward and reverse scans of the same process. A similar effect is sometimes observed with static linear transit calculations where forward and backward scans do not provide the same picture.
40. Animations of all the presented molecular dynamics simulations (forward scans) can be found at our research group's world wide web home page at 〈http://www.chem.ucalgary.ca/groups/ziegler〉.
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46. 6
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50. 3).
51. Relevant geometric parameters from the optimized geometry of the allyl-dihydrogen complex are as follows: H-H distance = 0.83 Å; Ti-H distances = 1.87, 1.87 Å; and C-C distances = 1.38, 1.40 Å.
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56. 71
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67. The most preferrable rate of long chain branching as specified in ref 5 is 1-2 long chain branches per 1000 C.
68. In actuality it was through the CP-MD simulations that the backside alkyl σ-bond metathesis channel was discovered.
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72. The reason for this discrepancy was our intent to use the largest most realistic model for the growing chain that we could computationally afford. At the time, this was an ethyl chain for the static calculations and a propyl chain for the molecular dynamics calculations. Since the time the static calculations were initiated, we have improved the efficiency of our static (ADF) code by over a factor of 2.