ChemInform Abstract: 1‐Aminodiazaphosphene, Synthesis, Crystal Structure, Bonding Properties, and Reactivity of a Derivative.

Dressler, U; Niecke, Edgar; Pohl, Siegfried; Saak, W.; Schoeller, Wolfgang W.; Schaefer, Hans-Jochen

doi:10.1002/chin.198651235

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“…Excess of DBU was removed under oil pump vacuum at 40°C. (4) 296 (5) 41 69(5) 722(5) 3793(4) 51 09 (5) 1801 (4) 4128 (5) 6397 (4) 7547 (4) 7390 (4) 6221 (4) 1574 (3) 0 -53 (1) 925 ( 1 ) 1344 ( 1 ) 2342 ( 1 ) 937 ( 1 ) 2440(2) 3072 (2) 2538 (2) 5(2) 774 (3) 1676 (2) -1 188 (2) -1701 (2) -1426 (2) -1355 (2) 300 (2) 2 W ) 61 (2) 1227 (2) 1776 ( 1 ) 4069 ( 1 ) 1821 (2) 625 (2) …”

Section: Preparation Of Tbu2p-p=n-nr2 ( 3 )mentioning

confidence: 99%

“…In contrast to 1-aminodiazaphosphene, tmp-P=N-N(SiMe& 4 [5], in 3 the bis (trimethylsily1)amino group is coplanar with the central P,-system, thus allowing the formation of a 4-electron 3-center-(PNN) p,-system (111, Scheme 3). This is further corroborated by the shortening of the N-N bond, 138 pm, and the widening of the P-N-N angle, 124", compared to 4, 150 pm, 107" [5]. The P-P bond distance, 220 pm, is in accord with the order of unity, while the valence angle at the u2-phosphorus, 95", is the smallest found so far in iminophosphanes [6].…”

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confidence: 98%

“…There, the PN double bond is also very long (160 pm [5]), but the bis-silylaminogroup (at N) is orthogonal to the central wsystem [9]. Thus, it is incapable of allylic resonance.…”

mentioning

confidence: 99%

“…The case at hand may be compared with structural findings on 4 [5]. There, the PN double bond is also very long (160 pm [5]), but the bis-silylaminogroup (at N) is orthogonal to the central wsystem [9].…”

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1‐Phosphinodiazaphosphene: Synthesis, crystal structure, and bonding properties

Altmeyer

Niecke

Nieger

et al. 1990

Heteroatom Chemistry

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Dedicated to Professor Alfred Schmidpeter on the occasion of his 60th birthday. ABSTRACTThe iminophosphane, ~Bu~P-P=N-NR~ (R=SiMeJ, produced by base-catalyzed elimination of ClSiMe3 from the corresponding phosphane, possesses an unusually long PN bond (162 pm), which is in accord with quantum chemical calculations.According to quantum chemical calculations uelectron-push-pull substitution exerts unexpected bonding effects on P(II1) double bonded systems [l]; in iminophosphanes a strong c+-acceptor at phosphorus tends to shorten the PN double bond (case I) with concomitant linearization of the nitrogen environment, while a u-acceptor at the nitrogen does the opposite; it lengthens the PN bond (case 11). Hitherto only case I has been experimentally verified in detail [2] (Scheme 1). Here we report on the synthesis, structural elucidation, and quantum chemical investigations on its bonding properties of a novel 1 -phosphinodiazaphosphene (3). Reaction of the hydrazino(dich1oro)phosphane 1 [3] with one equivalent of lithium-bis-t.butylphosphide [4] produces the hydrazino-diphosphane 2. Treatment of 2 with DBU results in a smooth elimination of chlorosilane with formation of the 1-phosphinodiazaphosphene 3 (Scheme 2). The constitution of both compounds was proven by means of mass and NMR spectral data, and X-ray structural analysis for 3. The deshielding of the low field 31P signal of the AX spectrum of 3 (6 = 429) is consistent with the formation of the PN-double bond system. The structure of 3 is illustrated in Figure 1. In contrast to 1-aminodiazaphosphene, tmp-P=N-N(SiMe& 4 [5], in 3 the bis (trimethylsily1)amino group is coplanar with the central P,-system, thus allowing the formation of a 4-electron 3-center-(PNN) p,-system (111, Scheme 3). This is further corroborated by the shortening of the N-N bond, 138 pm, and the widening of the P-N-N angle, 124", compared to 4, 150 pm, 107" [5]. The P-P bond distance, 220 pm, is in accord with the order of unity, while the valence angle at the u2-phosphorus, 95", is the smallest found so far in iminophosphanes [6]. However, most remarkable is the unusually long PN double bond distance, 162 pm, which is even longer than found in bis(amin0)phosphenium cations [7].

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Section: Preparation Of Tbu2p-p=n-nr2 ( 3 )mentioning

confidence: 99%

mentioning

confidence: 98%

“…There, the PN double bond is also very long (160 pm [5]), but the bis-silylaminogroup (at N) is orthogonal to the central wsystem [9]. Thus, it is incapable of allylic resonance.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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