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BY-NC-ND 3.0 license Open Access Published by De Gruyter (O) May 13, 2017

Crystal structure of 1,1-bis(η5-adamantylcyclopentadienyl)-3-phenyl-2-trimethylsilyl-2,3-dihydroisotitanazole, C42H55NSiTi

  • Manfred Manßen , Marc Schmidtmann and Rüdiger Beckhaus EMAIL logo

Abstract

C42H55NSiTi, triclinic, P1̅ (no. 2), a = 9.2556(4) Å, b = 12.5048(5) Å, c = 15.7350(7) Å, α = 69.6151(13)°, β = 85.3502(14)°, γ = 83.8861(14)°, V = 1695.51(13) Å3, Z = 2, Rgt(F) = 0.0334, wRref(F2) = 0.0885, T = 100(2) K.

CCDC no.:: 1543470

The asymmetric unit of the title crystal structure is shown in the figure. Hydrogen atoms are omitted for clarity. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Green block
Size:0.36 × 0.24 × 0.16 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:3.2 cm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω
2θmax, completeness:70°, >99%
N(hkl)measured, N(hkl)unique:32114, 32114
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 28454
N(param)refined:418
Programs:Bruker programs [1], SHELX [2]
Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Ti10.35939(2)0.25596(2)0.27314(2)0.00837(3)
Si10.62020(3)0.37181(2)0.33914(2)0.01040(5)
N10.44596(8)0.37739(6)0.30401(5)0.01022(11)
C10.28537(9)0.24738(7)0.12846(5)0.01080(13)
C20.39936(9)0.16056(7)0.15786(6)0.01219(14)
H20.39190.08100.17200.015*
C30.52689(9)0.21123(8)0.16296(6)0.01355(14)
H30.61770.17160.18390.016*
C40.49456(9)0.33129(8)0.13116(6)0.01312(14)
H40.56110.38690.12430.016*
C50.34655(9)0.35377(7)0.11154(6)0.01199(14)
H50.29550.42750.09050.014*
C60.12832(9)0.23142(7)0.11884(6)0.01076(13)
H60.07570.22150.17880.013*
C70.05216(9)0.33657(7)0.04764(6)0.01313(14)
H70.06340.40690.06220.016*
C8−0.11038(10)0.31994(8)0.04948(6)0.01599(15)
H8A−0.15530.31140.11050.019*
H8B−0.16010.38800.00490.019*
C9−0.12868(10)0.21289(8)0.02625(6)0.01504(15)
H9−0.23450.20210.02770.018*
C10−0.05203(10)0.10865(8)0.09668(6)0.01559(15)
H10A−0.06470.03860.08330.019*
H10B−0.09620.09970.15800.019*
C110.11101(9)0.12405(7)0.09462(6)0.01308(14)
H110.16020.05520.14010.016*
C120.11990(10)0.35046(9)−0.04759(6)0.01712(16)
H12A0.22440.3623−0.04970.021*
H12B0.07130.4184−0.09280.021*
C13−0.05990(11)0.22650(10)−0.06878(6)0.01944(18)
H13A−0.10930.2935−0.11450.023*
H13B−0.07190.1576−0.08390.023*
C140.17929(10)0.13840(9)−0.00047(7)0.01726(16)
H14A0.16960.0688−0.01520.021*
H14B0.28420.1487−0.00200.021*
C150.10269(10)0.24305(10)−0.07083(6)0.01853(17)
H150.14750.2523−0.13270.022*
C160.26417(9)0.17175(7)0.43676(5)0.01074(13)
C170.40601(9)0.12254(7)0.42704(6)0.01205(14)
H170.48830.12890.45680.014*
C180.40638(10)0.06196(7)0.36568(6)0.01368(14)
H180.48830.02170.34680.016*
C190.26247(10)0.07250(7)0.33782(6)0.01382(14)
H190.22960.03850.29830.017*
C200.17656(9)0.14250(7)0.37912(6)0.01259(14)
H200.07640.16630.37000.015*
C210.21769(9)0.24104(7)0.49726(6)0.01104(13)
H210.25530.31810.46780.013*
C220.05111(9)0.25946(7)0.51189(6)0.01295(14)
H220.00590.29460.45170.016*
C230.01917(11)0.34082(8)0.56658(7)0.01754(16)
H23A0.06060.41460.53300.021*
H23B−0.08730.35620.57450.021*
C240.08556(10)0.28741(8)0.66007(6)0.01574(15)
H240.06360.34080.69510.019*
C250.25063(10)0.26704(8)0.64621(6)0.01523(15)
H25A0.29530.23300.70590.018*
H25B0.29240.34090.61330.018*
C260.28435(9)0.18613(7)0.59168(6)0.01133(13)
H260.39210.17220.58350.014*
C27−0.01438(10)0.14560(8)0.56502(6)0.01439(15)
H27A−0.12100.15930.57370.017*
H27B0.00450.09250.53040.017*
C280.02163(10)0.17311(8)0.71235(6)0.01608(15)
H28A−0.08480.18610.72220.019*
H28B0.06490.13830.77240.019*
C290.21932(10)0.07186(7)0.64333(6)0.01286(14)
H29A0.24080.01930.60840.015*
H29B0.26400.03570.70280.015*
C300.05427(10)0.09197(8)0.65778(6)0.01349(14)
H300.01300.01730.69190.016*
C310.34483(9)0.47561(7)0.30921(6)0.01141(13)
H310.33930.47390.37340.014*
C320.38784(9)0.59398(7)0.24793(6)0.01142(13)
C330.42535(10)0.61815(8)0.15569(6)0.01477(15)
H330.42830.55910.13040.018*
C340.45840(10)0.72734(8)0.10045(6)0.01726(16)
H340.48550.74220.03810.021*
C350.45181(11)0.81519(8)0.13659(7)0.02050(18)
H350.47350.89010.09890.025*
C360.41346(12)0.79252(8)0.22781(7)0.02068(18)
H360.40830.85210.25260.025*
C370.38233(10)0.68227(8)0.28334(7)0.01584(15)
H370.35710.66730.34590.019*
C380.73137(10)0.23770(8)0.33748(8)0.01997(18)
H38A0.67240.17220.36330.030*
H38B0.81710.22560.37350.030*
H38C0.76260.24540.27480.030*
C390.73053(11)0.49011(9)0.26585(7)0.02071(18)
H39A0.73550.49100.20310.031*
H39B0.82900.47770.28800.031*
H39C0.68480.56360.26800.031*
C400.61472(12)0.37536(11)0.45757(7)0.0241(2)
H40A0.56260.44720.45910.036*
H40B0.71420.37020.47660.036*
H40C0.56440.31060.49890.036*
C410.19439(9)0.46138(7)0.28591(6)0.01302(14)
H410.1172(15)0.5245(12)0.2843(9)0.018(3)*
C420.17073(9)0.37173(7)0.26282(6)0.01207(14)
H420.0735(16)0.3664(13)0.2483(10)0.022(4)*

Source of material

All reactions were carried out under a dry nitrogen atmosphere using Schlenk-technique. Bis(adamantylidenepentafulvene)titanium was prepared by procedures reported previously [3, 4] . Bis(adamantylcyclopentadienyl)titanium-η2(N-benzylidenetrimethylsilylamine) was prepared by reaction of bis(adamantylidenepentafulvene)titanium with N-benzyltrimethylsilylamine as described for N-methylanilines at 60 °C for 3 d [4]. For the target compound a suspension of bis(adamantylcyclopentadienyl)titanium-η2-(N-benzylidenetrimethylsilylamine) (250 mg, 0.385 mmol) in 10 mL n-hexane was stirred under acetylene (1 atm.) for 15 min at room temperature, forming a brown suspension. The brown product was separated, washed with n-hexane and dried in vacuum.

Experimental details

The measured crystal was twinned non-merohedrally. The data were processed accordingly and refined against F2 in the HKLF5 format of the SHELX program [2]. All hydrogen atoms were located in the difference Fourier syntheses, and subsequently fixed to geometric positions using appropiate riding models.

Comment

Titanaaziridines are used in a variety of organic synthesis methods [5, 6] . In this context, the hydroaminoalkylation of alkenes, in which the insertion of the alkene into the Ti—C bond of the titanaaziridine is supposed to be the C—C forming step [7], [8], [9], [10], is likely the most important one. To the best of our knowledge, reactions of titanaaziridines and alkynes in the catalytic hydroaminoalkylation have not been reported until now. However, in stochiometric reactions there are a few examples of 5-membered ring insertion products [4, 11, 12]. Usually, such products are generated from mono and doubly aryl, alkyl- and trimethylsilyl-substituted alkynes. Here, we present the crystal structure of a dihydroisotitanazole, which was synthesized from bis(adamantylcyclopentadienyl)titanium-η2(N-benzylidene-trimethylsilylamine) and acetylene. This is the first structurally characterized dihydroisotitanazole employing the smallest possible substituted alkyne acetylene.

The Ti1—N1 (2.0049(7) Å) and the Ti1—C42 (2.1248(9) Å) bonds are in the expected range of dihydroisotitanazoles [4, 12] . The former acetylene C—C triple bond is now elongated to a typical C—C double bond with 1.3363(12) Å between C41—C42 in the insertion product [13]. The newly formed bond C31—C41 (1.5120(12) Å) is in accordance with a single bond [13]. The 5-membered ring (Ti1-N1-C31-C32-C42) is almost planar. Due to the strain of the ring, the angle N1—Ti1—C42 (81.34(3)°) differs significantly from the angle of an ideal pentagon (108°). Consequently, the titanium center has a distorted tetrahedral coordination.

References

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Received: 2016-12-19
Accepted: 2017-4-18
Published Online: 2017-5-13
Published in Print: 2017-7-26

©2017 Manfred Manßen et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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