Syntheses, Crystal Structure and Reactivity of Tin(II) Bis[<i>N</i>‐(diphenylphosphanyl)(2‐pyridylmethyl)amide]

Olbert, Dirk; Kalisch, Alexander; Görls, Helmar; Ondík, Irina Malkin; Reiher, Markus; Westerhausen, Matthias

doi:10.1002/zaac.200801328

Cited by 9 publications

(7 citation statements)

References 39 publications

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“…The other lithium cation (Li1) is situated in a trigonal‐planar environment and binds to two nitrogen atoms and one tetrahydrofuran molecule. Similar structures of N ‐trialkylsilyl‐substituted (2‐pyridylmethyl)amides were observed earlier,5 whereas lithium (diphenylphosphanyl)(2‐pyridylmethyl)amide adopts a different structure 28. The bridging fashion of the amide functionality and the higher coordination number of the nitrogen atoms lead to significant changes of the structural parameters.…”

Section: Resultssupporting

confidence: 67%

Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

et al. 2010

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A two-step synthesis allows the preparation of [α-(2-pyridyl)-benzyl]amine (1) in good yield. Phosphanylation in the presence of triethylamine gives (diphenylphosphanyl)[α-(2-pyridyl)benzyl]amine (2), which crystallizes as a racemate in the centrosymmetric triclinic space group P1. The P-N bond lengths exhibit an average value of 168.3 pm. Lithiation of 2 with n-butyllithium yields dimeric semi(tetrahydrofuran)lithium (diphenylphosphanyl)[α-(2-pyridyl)benzyl]amide (3) with the lithium atoms in different environments. One Li

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Section: Resultssupporting

confidence: 67%

Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

et al. 2010

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“…Similar to Fryzuk’s ( Si NPN )Li 2 (thf) 2 , one of the lithium ions in ( B )Li 2 (thf)(Et 2 O) is only three-coordinate, while the other is bound to the phosphine, forming a slightly distorted tetrahedron. The intermetallic separation of 2.48 Å and the Li1–P1 distance of 2.55 Å are both well within the usual boundaries for phosphine-coordinated μ 2 -Li 2 N 2 diamond cores. ,− …”

Section: Resultssupporting

confidence: 60%

Synthesis of NPN-Coordinated Tantalum Alkyl Complexes and Their Hydrogenolysis: Isolation of a Terminal Tantalum Hydride Incorporating a Doubly Cyclometalated NPN Scaffold

et al. 2017

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The closely related benzylene-linked diaminophosphines PhP(CHCH-o-NHPh) (AH) and PhP(CH-o-CHNHXyl) (BH with Xyl = 3,5-MeCH) were employed for the synthesis of tantalum(V) alkyls, which were then studied with respect to hydrogenolysis. In the case of AH, the tantalum trimethyl complex [Ta(A)Me] (1) and the tantalum hydrocarbyl complex [Ta(A)(CHSiMe)(η-EtC≡CEt)] (2) were prepared from the ligand's dilithium salt (A)Li(diox). Upon hydrogenolysis of 1 and 2, the formation of methane and SiMe, respectively, was observed, but well-defined tantalum hydrides could not be detected. In the case of BH, the cyclometalated species [Ta(B*)(NMe)] (3 with B* = κ-N,P,N,C-(PhP(CH-o-CHNXyl)(CH-o-CHNXyl))) was isolated and converted to the corresponding diiodo species [Ta(B*)I] (4). Treatment of 4 with LiCHSiMe resulted in the isolation of the corresponding dialkyl complex [Ta(B*)(CHSiMe)] (5), which was converted to the doubly cyclometalated monoalkyl complexes [Ta(B**)(CHSiMe)(PMe)] (6 with B** = κ-C,N,P,N,C-(PhP(CH-o-CHNXyl))) and [Ta(B**)(CHSiMe)(dmpe)] (7) via reaction with PMe and dmpe, respectively. In contrast to 5 and 6, 7 was found to react cleanly with dihydrogen to afford the corresponding terminal tantalum(V) hydride [Ta(B**)(H)(dmpe)] (8). Upon reaction of 7 with D, the deuteride [Ta(d-B**)(D)(dmpe)] (9) was obtained and found to contain deuterium atoms in the methine positions of both tantalaaziridine subunits. The partially deuterated derivatives [Ta(B**)(D)(dmpe)] (10) and [Ta(d-B**)(H)(dmpe)] (11) were generated via reaction of 8 and 9 with PhSiD and PhSiH, respectively. Prior to the addition of gaseous D or H, no H/D scrambling was observed in 10 or 11, indicating that the exchange of the methine positions proceeds via addition of D or H across the tantalaaziridine Ta-C bonds.

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“…DEI-mass spectra were obtained on a Finnigan MAT SSQ 710 system (2,4-dimethoxybenzyl alcohol as matrix), IR measurements were carried out on a Perkin-Elmer System 2000 FT-IR. Starting [(thf)-Fe{N(SiMe 3 ) 2 } 2 Cl], [36,41] Py-CH 2 -N(H)-PPh 2 (1), [28] and Py-C(Ph)-H-N(H)-PPh 2 [42] were prepared according to literature procedures. (4) …”

Section: Methodsmentioning

confidence: 99%

“…[27] In order to further elucidate the influence of the Nbound substituent, we investigated the reaction of ironbased metalation reagents with N-diphenylphosphanyl-picolylamine [28] which offers an additional Lewis base.…”

Section: P(o)-n(h)-ch 2 Py}] (5)mentioning

confidence: 99%

Influence of N‐Substitution on the Oxidation of 2‐Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) – Synthesis of Heteroleptic Iron(II) 2‐Pyridylmethylamides

et al. 2011

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The reaction of (thf)Fe[N(SiMe3)2]2Cl with (2‐pyridylmethyl)(diphenylphosphanyl)amine (1) in hot tetrahydrofuran (THF) yields dinuclear [(ClFe)2{μ‐N(SiMe3)2}{Ph2P(NCH2Py)2}] (2) and [ClFe{Ph2P(O)‐NCH2Py}]2 (3) with the oxygen atom stemming from THF degradation. The formation of 2 requires a P–N bond cleavage and reformation leading to the tetradendate diphenyl‐bis(2‐pyridylmethylamido)phosphonium ion. If this reaction of (thf)Fe[N(SiMe3)2]2Cl with 1 is performed at room temperature, no P–N bond cleavage is observed. Instead of that, ether degradation occurs yielding [Fe4(μ4‐O)(μ2‐Cl)2(Ph2P‐NCH2Py)4] (4) with a central oxygen‐centered iron tetrahedron as well as complex 3. Recrystallization of 3 from dichloromethane leads to addition of HCl and to the formation of [FeCl2·{Ph2P(O)‐N(H)‐CH2Py}] (5). The phosphonium ion of 2 is isoelectronic to the corresponding diphenyl‐bis(2‐pyridylmethylamino)silane (6). Lithiation of 6 followed by a metathetical reaction with (thf)2FeCl2 yields the trinuclear complex [Fe3Cl2{Ph2Si(NCH2Py)2}2] (7) with antiferromagnetic interactions.

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Syntheses, Crystal Structure and Reactivity of Tin(II) Bis[N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide]

Cited by 9 publications

References 39 publications

Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

Coordination Behavior of the (Diphenylphosphanyl)[α‐(2‐pyridyl)benzyl]amide Anion toward Lithium and Zinc Cations

Synthesis of NPN-Coordinated Tantalum Alkyl Complexes and Their Hydrogenolysis: Isolation of a Terminal Tantalum Hydride Incorporating a Doubly Cyclometalated NPN Scaffold

Influence of N‐Substitution on the Oxidation of 2‐Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) – Synthesis of Heteroleptic Iron(II) 2‐Pyridylmethylamides

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