Sulfur derivatives of 3‐methyl‐5‐phenyl‐1,2,4,3‐triazaphosphole

Schmidpeter, Alfred; Steinmüller, Franz; Karaghiosoff, Konstantin

doi:10.1002/hc.520050410

Cited by 10 publications

(2 citation statements)

References 19 publications

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“…All reactions and manipulations were carried out under dry argon by using Schlenk techniques. The azaphospholes [( η 6 ‐C 6 Me 6 )RuCl 2 ] 2 and [( η 5 ‐C 5 Me 5 )IrCl 2 ] 2 were prepared according to the literature methods 12–15. All solvents were purified by standard methods 16; dichloromethane was distilled from calcium hydride, and n ‐pentane was distilled from sodium.…”

Section: Methodsmentioning

confidence: 99%

Di‐ and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

Köhler¹,

Kammerer²,

Mayer³

et al. 2009

Zeitschrift anorg allge chemie

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The reaction of the azaphospholes 5‐methyl‐2‐phenyl‐1,2,3‐diazaphospole (PDAP) and 2‐methyl‐2‐phenyl‐1,2,4,3‐triazaphospole (PTAP) with the dimers [LMCl2]2 (LM = η6‐C6Me6Ru, η5‐C5Me5Ir) of ruthenium(II) and iridium(III) only occurs in presence of nucleophiles such as EtOH or H2O leading to their metal‐coordination after cleavage of the dimers. [(η6‐C6Me6)RuCl2]2 reacts with PDAP and EtOH in the molar ratio 0.5:1:1 to give the phosphorus‐coordinated complex (η6‐C6Me6)RuCl2(P‐PDAP·EtOH) (1). In the case of [(η5‐C5Me5)IrCl2]2, the triazaphosphole PTAP was used in the presence of EtOH or H2O yielding the analogous products (η5‐C5Me5)IrCl2(P‐PTAP·EtOH) (2) or (η5‐C5Me5)IrCl2(P‐PTAP·H2O) (3). In 1–3, the former aromatic azaphosphole (σ2,λ3‐P) has been converted by 1,2 addition of EtOH or H2O to their P=C or P=N double bond with the nucleophiles EtO– and OH– bonded to phosphorus (σ3,λ3‐P). Complexes 1–3 with a piano‐stool configuration were characterized by elemental analysis, 31P NMR spectroscopy and single‐crystal X‐ray diffraction.

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Section: Methodsmentioning

confidence: 99%

Di‐ and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

Köhler¹,

Kammerer²,

Mayer³

et al. 2009

Zeitschrift anorg allge chemie

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“…Their reactivity resides primarily in the P‫ס‬N bond. Oxidation by bromine [60] or sulfur [95] or complex formation [96,97] initiates its self-addition. Bicyclic or polycyclic oligomers are the result.…”

Section: Alfred Schmidpetermentioning

confidence: 99%

Molecules that we made: An essay on phosphorus chemistry

Schmidpeter¹

1999

Heteroatom Chem.

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The Interlocking of Salicylic Aldehydes and Ketones with a 2h‐1,2,4,3‐Triazaphosphole

Schmidpeter¹,

Steinmüller²,

Nöth

1996

Chem. Ber.

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Salicylic aldehyde (2a) adds to 2-methyl-5-phenyl-2H-compound forms dimers by a double hydrogen bond bet-1,2,4,3-triazaphosphole (1) to yield the bicyclic phosphonic ween two HN-PO units. Substituted salicylic aldehydes as amide 3a. The OH group adds to the P=N bond, the carbon well as ortho-hydroxyacetophenone and benzophenone reatom of the carbonyl group is inserted into the other P-N act in the same way. bond, and the phosphorus atom is oxidized. In the crystal the The phosphorus atom of a 2H-1,2,4,3-triazaphosphoIe such as 1 [1,2] is capable of both accepting and donating a pair of electrons. As a consequence it adds alcohols and other protic nucleophiles to its P = N bond and is oxidized by sulfur or halogen. Alcohols or phenols with appropriate additional functions can at the same time make use of both triazaphosphole reactivities. Glycols, 2-azido alcohols or oheterodienylphenols thus yield spirocyclic phosphorane~[~I. Salicylic aldehyde offers itself as another possible difunctional partner, although the nature of its second function is different. For the reaction with the triazaphosphole phosphorus atom it provides a nucleophilic hydroxyl and an electrophilic carbonyl group at a suitable three-bond distance. Results and DiscussionFrom the benzene solution of 2-methyl-5-phenyl-2H-1,2,4,3-triazaphosphole (1) and the 2-hydroxybenzaldehydes 2a-d (R' = H, R2-R5 = H, OMe, NOz) or 2-hydroxyacetophenone (2e) (R1 = Me, R2-R5 = H) or 2-hydroxybenzophenone (20 (R' = Ph, R2-R5 = H) products 3a-f precipitate. They are colorless except for the orangeyellow nitro derivative 3d. The reaction requires several days at ambient temperature for completion and of course proceeds more rapidly under reflux conditions. The compounds 3 consist of an equimolar combination of the two components as revealed by elemental analysis. It turned out, however, that the product in this case is not a spirocyclic A single-crystal X-ray analysis (see below) revealed the structure of example 3a. The NMR spectra of all other products (Tables 1 and 2) also correspond to those of 3a.The phenolic oxygen atom is bound to the phosphorus atom as expected, and the phosphorus atom is oxidized[*]X-ray structure analysis.

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Sulfur derivatives of 3‐methyl‐5‐phenyl‐1,2,4,3‐triazaphosphole

Abstract: ABSTRACT

Cited by 10 publications

References 19 publications

Di‐ and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

Di‐ and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

Molecules that we made: An essay on phosphorus chemistry

The Interlocking of Salicylic Aldehydes and Ketones with a 2h‐1,2,4,3‐Triazaphosphole

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