Die erste Si-H-B-Brücke: Kombination von 1,1-Organoborierung und Hydrosilylierung

Wrackmeyer, Bernd; Tok, Oleg L.; Bubnov, Yurii N.

doi:10.1002/(sici)1521-3757(19990115)111:1/2<214::aid-ange214>3.0.co;2-6

Angewandte Chemie

1999

DOI: 10.1002/(sici)1521-3757(19990115)111:1/2<214::aid-ange214>3.0.co;2-6

|View full text |Cite

Die erste Si-H-B-Brücke: Kombination von 1,1-Organoborierung und Hydrosilylierung

Bernd Wrackmeyer

Oleg L. Tok²,

Yurii N. Bubnov³

Abstract: Eindeutig aktiviert ist die Si‐H‐Bindung von 1, das durch Umsetzen von Triallylboran mit Bis(dimethylsilyl)ethin erhältlich ist, wegen der Nachbarschaft eines dreifach koordinierten Boratoms [Gl. (1)]. So reagiert 1 ohne Katalysator (!) in einer intramolekularen Hydrosilylierung zu 2.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2001

2007

Publication Types

Select...

Article5

Relationship

Self Cite2

Independent3

Authors

Journals

Cited by 25 publications

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

A Silyl Cation with a Three-Center Si-H-Si Bond

Müller

2001

Angew. Chem.

View full text Add to dashboard Cite

Three-center, two-electron bonds involving hydrogen as a bridging atom are a common feature in the chemistry of early main group metals. Several hydrido-bridged carbocations were identified by low-temperature NMR spectroscopy. [1] It was predicted that the isoelectronic silylium ions will even interact with methane, [2] and it was suggested that such interactions between a positively charged silicon atom and appropriately arranged alkyl groups on its substituents can be 60 kOe, which is very close to the expected value of 7.0 Nm B for a parallel alignment of the magnetic moments of two Ru III and one Mn II ion. Furthermore, a characteristic hysteresis loop is observed at 1.85 K but with negligible remanent magnetization (0.06 Nm B ) and coercive field (6 Oe). Although ferromagnetic Ru III ± Mn II interaction was also observed in two-dimensional (NBu 4 )[Mn II Ru III (ox) 3 ] via the oxalato bridges, no long-range ordering occurs down to 2 K. [4] We are currently investigating related 3d ± 4d and 4d ± 5d systems in order to understand the origin of the ferromagnetic behavior in 2. Experimental Section1: trans-Ph 4 P[Ru III (acac) 2 Cl 2 ] [12] (355 mg, 0.5 mmol) and KCN (325 mg, 5.0 mmol) were heated in refluxing methanol (30 mL) for 24 h. The solution was evaporated to dryness, and the residue was dissolved in CH 2 Cl 2 (10 mL). After filtration, the product was precipitated as a dark purple solid by adding diethyl ether. Yield: 225 mg (65 %). Crystals suitable for X-ray crystallography were obtained by slow diffusion of diethyl ether into a solution of 1 in CH 2 Cl 2 . IR (KBr): n Ä CN 2099 cm À1 ; UV/Vis (CH 3 CN): l max (lge) 349 (3.76), 407 sh (3.16), 540 (3.22); elemental analysis (%) calcd for C 36 H 34 N 2 O 4 RuP: C 62.60, H 4.96, N 4.06; found: C 62.96, H 5.05, N 4.21. 2: A mixture of MnClO 4´6 H 2 O (36 mg, 0.1 mmol) and 1 (69 mg, 0.1 mmol) was stirred in methanol (30 mL) at room temperature. The solution was filtered after 3 h, and slow evaporation of the filtrate afforded dark purple crystals. Yield: 34 mg (45 %). IR (KBr): n Ä CN 2125 cm À1 ; elemental analysis (%) calcd for Ru 2 MnN 4 C 24 O [7] a) Crystal data for 1 (C 36 H 34 N 2 O 4 RuP): M r 690.72, dark purple prisms, monoclinic, space group P2 1 /c (no. 14), a 7.727(8), b 27.541(8), c 15.645(9) , b 103.13(8)8, V 3242(3) 3 , F(000) 1420.00, Z 4, 1 calcd 1.415 g cm À3 , m(Mo Ka ) 5.74 cm À1 . Data were measured on a Rigaku AFC7R diffractometer with graphite-monochromatized Mo Ka radiation and a 12-kW rotating anode generator at 28.0 8C. Of the 3670 reflections measured, 3298 were unique (R int 0.053), and 1403 with I b 2 s(I) were observed. Data were corrected for Lorentzian and polarization effects. The structure was solved by direct methods (SHELXS86), and the full-matrix least-squares refinement converged to R 0.094 and R w 0.077 with a GOF of 3.91. b) Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication...

show abstract

A Silyl Cation with a Three-Center Si-H-Si Bond

Müller

2001

Angew. Chem.

View full text Add to dashboard Cite

show abstract

1-Boraadamantane: Reactivity Towards Di(1-alkynyl)silicon and -tin Compounds: First Access to 7-Metalla-2,5-diboranorbornane Derivatives

et al. 2001

Self Cite

View full text Add to dashboard Cite

1-Boraadamantane (1) reacts with di(1-alkynyl)silicon and -tin compounds 2 (Me2M(C...CR)2: M=Si; R=Me (a), tBu (b), SiMe3 (c); M=Sn, R=SiMe3 (e)) in a 1:1 ratio by intermolecular 1,1-alkylboration, followed by intramolecular 1,1-vinylboration, to give siloles 5a-c and the stannole 5e, respectively, in which the tricyclic 1-boraadamantane system is enlarged by two carbon atoms. Owing to the high reactivity of 1, a second fast intermolecular 1,1-alkylboration competes with the intramolecular 1,1-vinylboration as the second major step in the reaction if the substituent R at the C...C bond is small (2a) and/or if the M-C... bond is also highly reactive, as in 2d (M=Sn, R= Me) and 2e (M=Sn, R=SiMe3). This leads finally to the novel octacyclic 7-metalla-2,5-diboranorbornane derivatives 8a, 8d, and 8e, of which 8e was characterized by X-ray analysis in the solid state. 1,1,2,2-Tetramethyldi(1-propynyl)disilane, MeC...C-SiMe2SiMe2-C...CMe (3), reacts with 1 to give mainly a 1,2-dihydro-1,2,5-disilaborepine derivative 9 and the octacyclic compound 11, which is analogous to 8a but with an Me4Si2 bridge. All new products were characterized in solution by 1H, 11B, 13C, 29Si, and 119Sn NMR spectroscopy. For 8 and 11, highly resolved 29Si and 119Sn NMR spectra revealed the first two-bond isotope-induced chemical shifts, 2delta10/11B(29Si) and 2delta10/11B(119Sn) respectively, to be reported.

show abstract

Reactivity of 1,6-Bis(trimethylsilyl)-hexa-3-ene-1,5-diynes towards Triethylborane, Triallylborane, and 1-Boraadamantane: First Molecular Structure of a 4-Methylene-3-borahomoadamantane Derivative, and the First 6,8-Diborabicyclo[2.2.2]oct-2-ene Derivative

et al. 2002

Self Cite

View full text Add to dashboard Cite

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Die erste Si-H-B-Brücke: Kombination von 1,1-Organoborierung und Hydrosilylierung

Abstract: Eindeutig aktiviert ist die Si‐H‐Bindung von 1, das durch Umsetzen von Triallylboran mit Bis(dimethylsilyl)ethin erhältlich ist, wegen der Nachbarschaft eines dreifach koordinierten Boratoms [Gl. (1)]. So reagiert 1 ohne Katalysator (!) in einer intramolekularen Hydrosilylierung zu 2.

Cited by 25 publications

References 28 publications

A Silyl Cation with a Three-Center Si-H-Si Bond

A Silyl Cation with a Three-Center Si-H-Si Bond

1-Boraadamantane: Reactivity Towards Di(1-alkynyl)silicon and -tin Compounds: First Access to 7-Metalla-2,5-diboranorbornane Derivatives

Reactivity of 1,6-Bis(trimethylsilyl)-hexa-3-ene-1,5-diynes towards Triethylborane, Triallylborane, and 1-Boraadamantane: First Molecular Structure of a 4-Methylene-3-borahomoadamantane Derivative, and the First 6,8-Diborabicyclo[2.2.2]oct-2-ene Derivative

Contact Info

Product

Resources

About