Solution structure and reactivity of M+[Fe(CO)3(NO)]–, M = Na, K, or PPN [PPN =(Ph3P)2N]

Pannell, Keith H.; Chen, Yu Sen; Belknap, K.

doi:10.1039/c39770000362

Cited by 13 publications

(7 citation statements)

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“…It can be seen from the Tables I and II th a t th e re are several sign changes for V (207P b 1 3 C) and 2/ ( 2 0 7 P b 1 [16], from dif fering contributions of the s overlap integrals of the P b -F e bonds. T here are also several exam ples know n for which unexpected changes in leadelem ent spin-spin couplings w ere traced to the in fluence of relativistic effects [17].…”

Section: /'H H E T C O R Experim Entsmentioning

confidence: 95%

“…A lthough carbonyliron com plexes containing F e -P b bonds have been known for som e tim e [1], their N M R spectroscopic characterization has re ceived only scant atten tio n . In particular, the 207Pb N M R data, including chem ical shifts c>2()7Pb and coupling constants 17 (20 7 Pb"l7 Fe), n/ ( 2 0 7 P b I3 C) (n = 1, 2) and ,!y(2 0 7 P b 'H ) (n = 2, 3), are still missing.…”

mentioning

confidence: 99%

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Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂

Herberhold

Tröbs

Milius

et al. 1994

Zeitschrift Für Naturforschung B

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C om plexes of the types R3 P b -F e (C O )2Cp [R = Me (la ), Et (lb ), 'Pr (lc ), 'Bu (Id )]. R2 Pb[Fe(CO)2 Cp] 2 [R = Me (2a), Et (2b)], 'Pr2 (B r)P b -F e(C O )2Cp (3c) and [R2 PbFe(CO) 4 ] 2 [R = Me (4a), Et (4b), 'Pr (4c)], as well as the spiro-complexes Pb[Fe(C O )4 PbR2 ] 2 [R = Me (5a), Et (5b), 'Pr (5c)] and Pb[Fe(CO) 4 ] 4 (6) were studied by multinuclear magnetic reso nance spectroscopy ('FI, 1 3 C, 2<)7Pb NM R). For the first time, coupling constants '7(2 0 7 Pb5 7 Fe) were determ ined, covering a range between 33.5 (6) and 117 Hz (4a). The magnitude of the geminal coupling constants 12/ ( 2 0 7 Pb2ü7 Pb) I in the spiro-compounds 5 decreases from 1090.0 Hz (5a) to 377.0 Hz (5c). Tlie signs of the coupling constants '!7(2 0 7 Pb1 3 C(R)) (n = 1, 2) and ,'7(2H 7 P b1H {R)) (n = 2, 3) were determined by various 2 D NM R experiments. A m ong all known Pb(IV) compounds the lowest 207Pb nuclear magnetic shielding was found in Pb[Fe(C O) 4 ] 4 (6 ): d2')7Pb +3586.6. According to the single crystal X-ray structure determ i nation of 4b (orthorhombic; space group Pbca; a = 967.4, b = 1367.7, c = 1772.4 pm), the Pb2 Fe2 ring is planar with bond angles FePbFe = 102.8° and PbFePb = 77.2°, and there is a relatively short transannular distance of 340.8 pm between the two lead atoms.

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Section: /'H H E T C O R Experim Entsmentioning

confidence: 95%

mentioning

confidence: 99%

Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂

Herberhold

Tröbs

Milius

et al. 1994

Zeitschrift Für Naturforschung B

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“…2-q:l,2-q)-l,I-his (trimethylsilyl)buta-l.3-diyne] [p-methylenebis(diphenylphosphine)-P:P]dieobalt (19). To hexacdrbonylh ,-(1,2-q : 1,2-q)-1,4-bis(trimethylsilyl)buta-1,3-diyne]dicobalt [34] (1.64 g, 3.4 mmol) in degassed benzene (50 ml) was added bis(dipheny1phosphino)methane (dppm; 1.31 g, 3.4 mmol), and the mixture was refluxed under Ar for 12 h. Evaporation and FC (SiO,, CH2Cl,/hexane 9:1 and 8 :2) afforded 19 (2.34 g, 85%). (21).…”

Section: 12-diethynyl-y10-dihydro-ylo-ethenoanthracenementioning

confidence: 99%

“…The butadiyne complex 18 was first prepared as a model to test the Eglinton-Glaser oxidative coupling of (p -alkyne)dicobalt complexes bearing an additional free terminal alkyne group (Scheme 4 ) . Ligand [34] with dppm afforded 19 (85 YO) which was deprotected almost quantitatively at the uncomplexed alkyne group with Bu,NF in THF/MeOH 10: 1 (-+ 18). The butadiyne complex 20 was obtained as stable, deep red crystals when stronger desilylation conditions were used (Bu4NF in wet THF).…”

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confidence: 99%

Synthetic Routes to the Cyclo[n]carbons

Diederich¹,

Rubin

Chapman

et al. 1994

Helvetica Chimica Acta

116

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Cyclo[n]carbons (cyclo-C,) are n-membered monocyclic rings of sp-hybridized C-atoms with unique electronic structures resulting from two perpendicular systems of conjugated n-orbitals, one in-plane and one out-ofplane. Several synthetic approaches to generate cyclo-Clx from stable precursors were investigated. In a six-step sequence from anthracene, tris(anthraceno)hexadehydro[l8]annulene 5 was prepared and shown by laser-desorption time-of-flight mass spectrometry to generate C,, in three successive retro-Diels-Alder reactions, together with anthracene as the by-product. The attempted preparation of CIS by flash-vacuum pyrolysis of 5 using solventassisted sublimation only afforded anthracene next to polymers. The reaction of 1,6-bis(triisopropylsilyl)hexa-1,3,5-triyne with [Co,(CO),] followed by exchange of two CO groups for a bridging bis(dipheny1phos-phino)methane (dppm) ligand gave Co complex 22 which, after removal of the silyl groups, was oxidatively cyclized to afford the very stable trimeric and tetrameric macrocycles 6 and 7, complexes with cyclo-C,, and cyclo-C,,, respectively. An X-ray crystal structure established the identity of 6 and showed that the butadiyne units within the C,, core are considerably bent. Attempts to free cyclo-Clx from the coordinating metal atoms in 6 did not succeed, presumably due to the steric shielding of the Co-atoms by the dppm ligands. Low-temperature matrix isolation studies using IR and UVjVIS spectroscopy showed that irradiation of carbon oxide 2 (C&06) leads to ketene intermediates and, by subsequent loss of six CO molecules, presumably to cyclo-C,,.

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“…When TlHF was replaced by acetonitrile, only two vCO's (1895 and 1820 cm-I strong) and one vNO (1600 cni-') were present. The shift towards higher wave nurnbers of the strong absorptions corresponding to the vNO and in the opposite direction for-those corresponding to the vCO's under the intluence of a good coordinating solvent was also observed with the sodium salts of the same anion 15 (7) and of the unsubstituted one [Fe(C0)3(NO)]-1 (21). This was taken as evidence for the occurence in THF of an equilibrium between loose and tight ion pairs, and for a specific cation.. .O-nitrosyl interaction in the tight ion pairs.…”

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confidence: 78%

Synthesis and reactivity of iron nitrosyl hydrides substituted with triphenyl phosphine

Roustan¹,

Forgues²,

Mérour³

et al. 1983

Can. J. Chem.

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Protonation of anion 1 [Fe(CO)3(NO)]−, (Na+) in the presence of P(C6H5)3 yielded the iron nitrosyl hydrides 3 FeH-(CO)2(NO)(P(C6H5)3) and 4 FeH(CO)(NO)(P(C6H5)3)2 or the iron nitrosyl cation 5 [Fe(CO)2(NO)(P(C6H5)3)2]+, [Formula: see text] de- pending upon the conditions. Anions 12 (Li+),[Fe(CO)(NO)(P(C6H5)3)2]− and 15 (Li+),[Fe(CO)2(NO)(P(C6H5)3)]− were formed in the reactions of Li+, −HB(C2H5)313 with hydrides 4 and 3 respectively. Anions 15 resulted also from the reaction of cation 5 with an excess (at least 6 equivalents) of boron hydride 13 and from the reaction of anion 12 with CO at atmospheric pressure. Hydrides 3 and 4 were prone to ligand exchange reactions and could be interconverted easily. This is in contrast to the reluctance of the isoelectronic cobalt hydride CoH(CO)3(P(C6H5)3) to undergo further reaction with P(C6H5)3. Another striking difference between the iron nitrosyl hydrides and the isoelectronic cobalt carbonyl hydrides was found when the reactions which normally yield bimetallic derivatives were investigated. The nature of the decomposition products formed in the thermolysis of 3 and 4, in the reactions of 3 with olefins and dioxygen, and in the reduction reactions of cation 5 suggests that metallic dimers containing a (Fe(NO))2 unit are prone to fast CO and NO exchanges triggering an irreversible fragmentation into monometallic decomposition products, comprising invariably iron dinitrosyl derivatives.

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Solution structure and reactivity of M⁺[Fe(CO)₃(NO)]^–, M = Na, K, or PPN [PPN =(Ph₃P)₂N]

Cited by 13 publications

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Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂

Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂

Synthetic Routes to the Cyclo[n]carbons

Synthesis and reactivity of iron nitrosyl hydrides substituted with triphenyl phosphine

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Solution structure and reactivity of M+[Fe(CO)3(NO)]–, M = Na, K, or PPN [PPN =(Ph3P)2N]

Cited by 13 publications

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Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et2PbFe(CO)4]2

Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et2PbFe(CO)4]2

Synthetic Routes to the Cyclo[n]carbons

Synthesis and reactivity of iron nitrosyl hydrides substituted with triphenyl phosphine

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Solution structure and reactivity of M⁺[Fe(CO)₃(NO)]^–, M = Na, K, or PPN [PPN =(Ph₃P)₂N]

Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂

Carbonyliron-Lead Complexes: Multinuclear Magnetic Resonance Study in Solution and X-Ray Structure Determination of [Et₂PbFe(CO)₄]₂