M(CO)5(R3PTe)(M = Cr, Mo, W; R = But): the first stable tellurophosphorane complexes

Kühn, Norbert; Schümann, H. J.; Wolmershäuser, Gottheff

doi:10.1039/c39850001595

Cited by 32 publications

(38 citation statements)

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“…1) follows the expectations of stuctural phosphorus chemistry [8] and the predictions of the VSEPR rule [9]. On comparison with the carbene base adduct of PO 2 Cl (3) we see only minor changes in the structure of the PO 2 Cl fragment underlining the marked nucleophilicity of the carbene ligand there [10], and also the PO bond lengths and OϪPϪO' angles of the [PO 2 F 2 ] Ϫ anion in its alkali metal and ammonia salts [11,12] are very similar. The isoelectronic sulfuryl chloride molecule [13] exhibits the expected shortening of the bond lengths.…”

supporting

confidence: 77%

2-Chloro-1, 3-diisopropyl-4, 5-dimethylimidazolium Dichlorophosphate. First Structural Characterisation of the [PO2Cl2]— Anion [1]

Kühn

Abu‐Rayyan

Ströbele

2002

Z. anorg. allg. Chem.

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The X-ray structure of 2-Chloro-1,3-diisopropyl-4,5-dimethylimidazolium dichlorophosphate (2) (obtained from 2-chloro-1,3-diisopropyl-4,5-dimethylimidazolium chloride 1 and POCl 3 in the presence of water) is reported.Dichlorophosphates exist as stable organic salts, M[PO 2 Cl 2 ][2] and act in metal complexes as coordinating ligands [2,3]. Two structure reports of their salts have been mentioned, but they do not include a description of the anion apparently as a consequence from disordering problems [4]. We therefore present the structure of the imidazolium salt 2 obtained from the hydrolysis of POCl 3 [5] in the presence of 1 [6,7]. The salt 2 crystallizes in the orthorhombic space group Pnma, both the ring atoms of the cation and the PCl 2 fragment of the anion lying on crystallographic mirror planes. A view on the interionic distances reveals the presence of separated ions in the unit cell ( Fig. 1); in fact, the closest cation to anion ClϪCl distance [Cl(1)ϪCl(2) 508.2(1) pm] is out of range of the van der Waals radii and even longer than those observed both for the cations [Cl(1)ϪCl(1#) 497.0(1) pm] and the anions [Cl(2)ϪCl(2#) 467.4(1) pm] and even shorter than the closest cation to anion separation. This finding contrasts markedly to the significant ClϪCl interaction in 1 (315.9 pm [7]) and documents the low nucleophilicity of the PO 2 Cl 2 Ϫ anion towards the 2-chloroimidazolium ion. Comparing the structures of the cations in 1 and 2, we detect a change in the orientation of the isopropyl groups and the presence of intraionic CϪHϪCl hydrogen bridges [C(5)ϪH (5) 90(4), H(5)ϪCl(1) 277(3), C(9)ϪH(9) 93(3), H(9)ϪCl(1) 280(3) pm; C(5)ϪH(5)ϪCl(1) 123(2), H(5)ϪCl(1) C(1) 82.5(5), C(9)ϪH(9)ϪCl(1) 118(2), H(9)ϪCl(1)ϪC(1) 81.1(8)°] (Fig. 2) which may be influenced by the absence of interionic ClϪCl interactions in 2.Fig. 1 View on the elemental cell of 2.The structure of the [PO 2 Cl 2 ] Ϫ anion (Fig. 2, tab. 1) follows the expectations of stuctural phosphorus chemistry [8] and the predictions of the VSEPR rule [9]. On comparison with the carbene base adduct of PO 2 Cl (3) we see only minor changes in the structure of the PO 2 Cl fragment underlining the marked nucleophilicity of the carbene ligand there [10], and also the PO bond lengths and OϪPϪO' angles of the [PO 2 F 2 ] Ϫ anion in its alkali metal and ammonia salts [11,12] are very similar. The isoelectronic sulfuryl chloride molecule [13] exhibits the expected shortening of the bond lengths. The widening of the OϪSϪO' bond angle may reflect a lower bond order of the SO bond in comparison with the title anion. Comparison with structural data of [PO 2 Cl 2 ] Ϫ ligand complexes [14Ϫ16] reveals a minor change of the structure of the ligand on coordination apart from some differences in the OϪPϪO' angles. We therefore suggest the metal to oxygen bonds in the coordination compounds of the dichlorophosphate ligand to be mainly of electrostatic nature both in the terminal [14] and bridging [15] coordination mode.

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confidence: 77%

2-Chloro-1, 3-diisopropyl-4, 5-dimethylimidazolium Dichlorophosphate. First Structural Characterisation of the [PO2Cl2]— Anion [1]

Kühn

Abu‐Rayyan

Ströbele

2002

Z. anorg. allg. Chem.

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“…These results are consistent with earlier work which showed soluble iron to be a much more powerful oxidation catalyst than iron wire or iron powder (Brook and Matthews, 1951;Rowe et al, 1958;Kuhn, 1973), and the effect of soluble iron can be attributed to the redox reactions …”

Section: Catalysis By Solubie and Particulate Ironsupporting

confidence: 92%

“…The oxidation of a fully formulated lubricant oil in a fired engine represents a much more complex environment, but the trend is now to simulate these conditions more closely in the laboratory. Bench oxidation tests used within the oil industry have been reviewed (Hsu, 1981;Warne and Vienna, 1984), and attempts have been made to develop tests which correlate with the Sequence IIIC and IIID tests (Cecil, 1973;Kuhn, 1973;Hsu et al, 1982;Klaus et al, 1982). The roles of copper and iron have been investigated using a thin film 0888-5885/ 87 / 2626-1888$01.50/ 0 oxidation test (Clark et al, 1985), and it has been shown that the composition of the base stock, as well as the presence of succinimide dispersant and calcium high base number sulfonate, all affect the oxidation stability of a lube oil (Hsu and Lin, 1983).…”

Section: Role Of Additives and Transition Metals In Lubricating Oil Omentioning

confidence: 99%

Role of additives and transition metals in lubricating oil oxidation

Colclough¹

1987

Ind. Eng. Chem. Res.

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A bulk oil oxidation test has been used to investigate the pro-and antioxidant effects of iron and copper and also the effects of basic dispersants and detergents, zinc dithiophosphates, and other antioxidants. Lube oil stability is strongly influenced by the particular combinations and concentrations of transition metal or lube additive used. Zinc dithiophosphates, on their own, strongly inhibit iron-catalyzed oxidations, but their activity is greatly reduced in the presence of basic additives. Under certain conditions, soluble copper, even at very low concentrations, is a far more potent antioxidant than conventional aromatic amines or phenols. Proposed actions of copper as a radical scavenger and zinc dithiophosphates as

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“…Treatment of the dilithium reagent [Li(TMEDA)] 2 [tBuN(Te)P(-NtBu) 2 P(Te)NtBu)] (1) with one equivalent of AgI produced the silver(I) complex {(I)Ag[tBu(H)NP(-NtBu) 2 P(Te)N(H)tBu] 3 } (2) in toluene at −78 °C in low yield (14 %) (Scheme 2). The low yield is attributed to the 1:1 molar ratio of reactants (unreacted AgI was recovered) and partial decomposition (formation of elemental tellurium was observed).…”

Section: Resultsmentioning

confidence: 99%

“…Kuhn et al reported the first stable complex, M(CO) 5 (TePtBu 3 ), in 1985 and obtained the crystal structure of the chromium derivative. [2] More recently, du Mont et al were able to structurally characterize the first Ag(I) complexes of a trialkylphosphane telluride and showed that the tellurium-centered ligand may function in a bridging mode e.g. [ [3] However, silver(I) halide complexes had previously eluded characterization owing to facile decomposition.…”

Section: Introductionmentioning

confidence: 99%

A Silver(I) Iodide Complex of a Tellurophosphorane

Nordheider

Slawin

Woollins

et al. 2014

Zeitschrift anorg allge chemie

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The formation and structural characterization of the first coordination complex of the tellurophosphorane [tBu(H)NP(-NtBu) 2 P(Te)N(H)tBu] are presented. The silver(I) iodide complex(1) with AgI in toluene and characterized by X-ray analysis and multinuclear NMR spectroscopy.Complex 2 is comprised of three tellurophosphorane ligands coordinated to AgI in a distorted tetrahedral arrangement (102.90(3)-114.51 (5) o ). The P=Te bond distances of 2.3883 (13)

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M(CO)₅(R₃PTe)(M = Cr, Mo, W; R = Bu^t): the first stable tellurophosphorane complexes

Cited by 32 publications

References 1 publication

2-Chloro-1, 3-diisopropyl-4, 5-dimethylimidazolium Dichlorophosphate. First Structural Characterisation of the [PO2Cl2]— Anion [1]

2-Chloro-1, 3-diisopropyl-4, 5-dimethylimidazolium Dichlorophosphate. First Structural Characterisation of the [PO2Cl2]— Anion [1]

Role of additives and transition metals in lubricating oil oxidation

A Silver(I) Iodide Complex of a Tellurophosphorane

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