A novel pattern of dimerization for 1, 4‐diphospha‐1,3‐butadienes

Ionkin, Alex S.; Marshall, William J.

doi:10.1002/hc.10123

Cited by 9 publications

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“…The synthetic methodology used to prepare 1,4-diphospha-1,3-butadienes initially developed by R. Appel was used to synthesize 1,5-diphospha-1,4-pentadiene ( 2 ) . 2,4,6-Tri- tert -butylphenyllithium ( 3 ) was reacted with commercially available 1,3-bis(dichlorophosphino)propane ( 4 ) to form 1,3-bis(chloro(2,4,6-tri- tert -butylphenyl)phosphino)propane ( 5 ) (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene

et al. 2007

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Tri-tert-butylphenyl)-1H-[1,2]diphosphole (12) was isolated from the unintentional and unexpected dehydrohalogenation of 1,3-bis(chloro(2,4,6-tri-tert-butylphenyl)phosphino)propane ( 5) with DBN. 1H-[1,2]Diphosphole 12 has substantial bond delocalization within the diphosphole system. Remarkably, the shortest P-C bond in the ring (1.725(4) Å) is observed for a nominal P-C single bond with the tricoordinated phosphorus atom. The P-P distance (2.0750(18) Å) in 12 is closer to the value for a PdP bond than for a P-P bond. The sum of the bond angles at the tricoordinated phosphorus atom in 12 is 351.3°, making 12 the most planar 1H-[1,2]diphosphole known to date. The 31 P NMR spectrum of 12 contains very similar chemical shifts for the tri-and dicoordinated phosphorus atoms (90.83 and 133.80 ppm), with a large P-P coupling constant ( 2 J PP ) 528.2 Hz). This is further evidence of significant delocalization of the lone pair electrons of the tricoordinated phosphorus into the ring system and is consistent with the aromaticity of the 1H-[1,2]diphosphole ring in 12. The reaction between ruthenium carbonyl and 8-{(2,4,6-tri-tert-butylphenyl)-[3-(2,4,6-tri-tert-butylphenylphosphanylidene)propyl]phosphanyl}-2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine (8), which is the second product from the unexpected dehydrohalogenation, resulted in the formation of complex 27, with a novel η 2 -coordination mode between ruthenium and the phosphaalkene. The P-C bond in the three-membered ring of 27 is substantially lengthened by η 2 -coordination, from 1.650(3) Å in the parent ligand to 1.775(3) Å in complex 27.

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Section: Resultsmentioning

confidence: 99%

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene

et al. 2007

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“…The diphosphabutadiene (244) has been shown to undergo an unusual [2þ4] cyclodimerisation to form (245). 708 The diphosphinidenecyclobutenes (246) continue to attract interest as diphosphabutadiene ligands for transition metal ions and related catalyst systems. 709,710 Metal complexes of 1,4-diphosphabutadienes, 711 2,3-diphosphabutadienes, 712 and 1-phospha-buta-1,3-dienes 713 have also been investigated.…”

Section: P P -Bonded Phosphorus Compoundsmentioning

confidence: 99%

Phosphines and Related Tervalent Phosphorus Systems

2006

Organophosphorus Chemistry

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“…The ligand has a similar geometry to that of the free 1,4-diphosphabutadiene. 5 It has a backbone that is localized and exhibits P-C and C-C bond lengths that are in the normal ranges for double and single interactions, respectively. 6 The phosphorus centers of the …”

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Crystal Structure of 1,4-Bis(triiodogallium(III))-1,4-bis(2,4,6-tri-tert-butylphenyl)-1,4-diphosphabuta-1,3-diene

et al. 2008

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A novel pattern of dimerization for 1, 4‐diphospha‐1,3‐butadienes

Abstract: A new example of [2+4] cycloadditionof the low-coordinated diphospha-analog of butadiene protected with a 2,4-di-tert-butyl-6-methylphenyl group has been described. X-ray structure investigations of monomer 4b and dimer 5a have been reported for the first time. C

Cited by 9 publications

References 16 publications

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Phosphines and Related Tervalent Phosphorus Systems

Crystal Structure of 1,4-Bis(triiodogallium(III))-1,4-bis(2,4,6-tri-tert-butylphenyl)-1,4-diphosphabuta-1,3-diene

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A novel pattern of dimerization for 1, 4‐diphospha‐1,3‐butadienes

Abstract: A new example of [2+4] cycloadditionof the low-coordinated diphospha-analog of butadiene protected with a 2,4-di-tert-butyl-6-methylphenyl group has been described. X-ray structure investigations of monomer 4b and dimer 5a have been reported for the first time. C

Cited by 9 publications

References 16 publications

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η2-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η2-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Phosphines and Related Tervalent Phosphorus Systems

Crystal Structure of 1,4-Bis(triiodogallium(III))-1,4-bis(2,4,6-tri-tert-butylphenyl)-1,4-diphosphabuta-1,3-diene

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Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene

Aromatic 1H-[1,2]Diphosphole with a Planar Tricoordinated Phosphorus, Plus η²-Coordination Mode between Ruthenium(0) and a Phosphaalkene