Transition Metal-Substituted Diphosphenes. 35. On the Reactivity of Metallodiphosphenes (.eta.5-C5Me5)(CO)2FeP:PR (R = C(SiMe3)3, 2,4,6-t-Bu3C6H2) Toward Isocyanides. Formation and Structures of Iminodiphosphiranes and 2,4-Diimino-1,3-diphosphetanes

Weber, Lothar; Buchwald, Susanne; Lentz, Dieter; Stamm, Oliver; Preugschat, Dagmar; Marschall, Robert

doi:10.1021/om00023a049

Cited by 18 publications

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“…The [Cp*(CO) 2 Fe] groups are oriented trans to each other, featuring two different iron−phosphorus single bonds (Fe(1)−P(1) = 2.3057(13) Å and Fe(2)−P(2) = 2.2296(12) Å). The longer Fe−P bond is quite comparable to the Fe−P separations in the 2,4-diimino-1,3-diphosphetane 5 (2.303(1) Å) …”

Section: Resultsmentioning

confidence: 76%

“…The longer Fe-P bond is quite comparable to the Fe-P separations in the 2,4-diimino-1,3-diphosphetane 5 (2.303(1) Å). 16 Usually, Fe-P bond distances in low-valent iron carbonyls fall in the range 2. 11-2.37 Å.…”

Section: Resultsmentioning

confidence: 99%

“…This assumption is further confirmed by the geometry at P(2) in comparison to that of the phosphorus atoms in II. P(2) displays the (3) 28(1) C (6) 4478 (5) 9038 (3) 6663 (3) 38(1) C (7) 3380 (5) 10312 (3) 8358 (3) 40(1) C(8) 3830 (5) 8729 (4) 10234 (3) 43(1) C(9) 5466 (5) 6466 (3) 9664 (3) 48(1) C (10) 5722 (5) 6598 (3) 7486 (3) 44(1) C(11) 998 (4) 8480 (3) 9436 (3) 27(1) C(12) 2406 (4) 6544 (3) 9274 (3) 26(1) C (13) 2412 (4) 7046 (3) 6663 (3) 26(1) C (14) 426 (4) 6587 (3) 8036 (3) 25(1) C (15) 308 (4) 3404 (3) 7570 (3) 28(1) C (16) 1569 (5) …”

Section: Resultsmentioning

confidence: 99%

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

et al. 1996

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Reaction of the lithoxy phosphaalkyne (DME) 2 LiOCtP (1) with 1 equiv of the complexes 3a-c) as red amorphous solids in 32-37% yield. By treatment with ((Z)-cyclooctene)-Cr(CO) 5 , compound 3a was converted into the red complex Cp*(CO) 2 FeP[Cr(CO) 5 ]C(O)P-[Fe(CO) 2 Cp*]C(O) (4). Constitutions and configurations of 3a-c and 4 were determined by elemental analyses and spectra (IR, 1 H, 13 C, and 31 P NMR, MS). The molecular structure of 4 was established by a single-crystal X-ray analysis.

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Section: Resultsmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

et al. 1996

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“…17 Threemembered rings like 24c,d were also isolated when the metal-substituted diphosphene 23b was reacted with phenyl or trifluoromethyl isocyanide; the same holds for the reaction of the latter component with the analogous substrate (23c  24e). 18 However, treatment of 23c with several aryl 18 and alkyl isocyanides 19 led directly to 1,3-diphosphetanediimines like 25a-f; the transient compounds 24f-k, being prone to P-P fission (cf. Section 3.1), were detected spectroscopically.…”

Section: [1+2] Cycloaddition Of Isocyanides To Double Bond Systems Anmentioning

confidence: 99%

Four-membered rings from isocyanides: Developments since the mid 1980s

Moderhack

2014

Arkivoc

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“…One of the few fragments for which several M–PR n complexes have been synthesized is the classic iron system, (CO) 2 FeCp † (Figure , Cp † = Cp or Cp*; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl). Iron–phosphorus complexes of the type (CO) 2 Fe(PR n )Cp † are primarily accessed via salt metathesis with the iron metalate Na[(CO) 2 FeCp † ] and include iron-phosphido (Fe–PR 2 ), − phosphinidene (FePR), , iminophosphanyl (Fe–PNR), diphosphenyl (Fe–PPR), , and phosphaalkenyl (Fe–PCR 2 ) ,− complexes. The Fe–P bonds in these complexes have minimal π-character, a consequence of the filled a″orbital in the d 6 [(CO) 2 FeCp † ] + fragment (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Panoply of P: An Array of Rhenium–Phosphorus Complexes Generated from a Transition Metal Anion

Hales,

Rajeshkumar,

Shiau

et al. 2024

Inorg. Chem.

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We expand upon the synthetic utility of anionic rhenium complex Na[(BDI)ReCp] (1, BDI = N,N '-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) to generate several rhenium−phosphorus complexes. Complex 1 reacts in a metathetical manner with chlorophosphines Ph 2 PCl, Me NHP-Cl, and OHP-Cl to generate XL-type phosphido complexes 2, 3, and 4, respectively ( Me NHP-Cl = 2-chloro-1,3-dimethyl-1,3,2diazaphospholidine; OHP-Cl = 2-chloro-1,3,2-dioxaphospholane). Crystallographic and computational investigations of phosphido triad 2, 3, and 4 reveal that increasing the electronegativity of the phosphorus substituent (C < N < O) results in a shortening and strengthening of the rhenium−phosphorus bond. Complex 1 reacts with iminophosphane Mes*NPCl (Mes* = 2,4,6-tritert-butylphenyl) to generate linear iminophosphanyl complex 5. In the presence of a suitable halide abstraction reagent, 1 reacts with the dichlorophosphine i Pr 2 NPCl 2 to afford cationic phosphinidene complex 6 + . Complex 6 + may be reduced by one electron to form 6 • , a rare example of a stable, paramagnetic phosphinidene complex. Spectroscopic and structural investigations, as well as computational analyses, are employed to elucidate the influence of the phosphorus substituent on the nature of the rhenium−phosphorus bond in 2 through 6. Furthermore, we examine several common analogies employed to understand metal phosphido, phosphinidene, and iminophosphanyl complexes.

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Transition Metal-Substituted Diphosphenes. 35. On the Reactivity of Metallodiphosphenes (.eta.5-C5Me5)(CO)2FeP:PR (R = C(SiMe3)3, 2,4,6-t-Bu3C6H2) Toward Isocyanides. Formation and Structures of Iminodiphosphiranes and 2,4-Diimino-1,3-diphosphetanes

Cited by 18 publications

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

Four-membered rings from isocyanides: Developments since the mid 1980s

Panoply of P: An Array of Rhenium–Phosphorus Complexes Generated from a Transition Metal Anion

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Transition Metal-Substituted Diphosphenes. 35. On the Reactivity of Metallodiphosphenes (.eta.5-C5Me5)(CO)2FeP:PR (R = C(SiMe3)3, 2,4,6-t-Bu3C6H2) Toward Isocyanides. Formation and Structures of Iminodiphosphiranes and 2,4-Diimino-1,3-diphosphetanes

Cited by 18 publications

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp*(CO)2FeP[Cr(CO)5]C(O)P[Fe(CO)2Cp*]C(O) (Cp* = η5-C5Me5)

Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp*(CO)2FeP[Cr(CO)5]C(O)P[Fe(CO)2Cp*]C(O) (Cp* = η5-C5Me5)

Four-membered rings from isocyanides: Developments since the mid 1980s

Panoply of P: An Array of Rhenium–Phosphorus Complexes Generated from a Transition Metal Anion

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Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)

Synthesis of 1,3-Dimetallo-1,3-diphosphetane-2,4-diones. X-ray Structure Analysis of Cp(CO)₂FeP[Cr(CO)₅]C(O)P[Fe(CO)₂Cp]C(O) (Cp* = η⁵-C₅Me₅)