Carbon-hydrogen cleavage versus nitrogen-nitrogen cleavage in .mu.3-.eta.2 azoalkane ligands on the M3(CO)9 clusters of iron, ruthenium, and osmium

Hansert, Bernhard; Tasi, M.; Tiripicchio, A.; Camellini, Marisa Tiripicchio; Vahrenkamp, H.

doi:10.1021/om00058a023

Cited by 19 publications

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“…21 Multimetal interactions involving both ends of hydrazido(-1) ligands have been observed in Ru 3 carbonyl cluster complexes. [43][44][45][46][47][48] The N-N bond distances in 2-4 are similar and range from 1.455(7) to 1.496(10) Å consistent with the single N-N bond in free hydrazines (1.45-1.46 Å). 49,50 The side-bonded bridging coordination mode of the MeNNMe unit in 1 suggests the presence of either a hydrazido(2-) or a diazo ligand.…”

Section: Discussionmentioning

confidence: 89%

“…Closely related [(dppm-H)Pt(μ-NHNH 2 )] 2 LiBF 4 also shows this bonding mode, but with a Li−N interaction with the free end of the hydrazido ligands − …”

Section: Discussionmentioning

confidence: 96%

“…Reductive cleavage of the Fe analogues of 1 to diimido or diamido complexes by addition of an Fe(CO) 3 fragment 61 or dihydrogen 62 have been reported, as have several other examples of diazo cleavage. 45,47,53,[63][64][65][66][67] The lack of success with 1 may be due to the instability of the expected diimido product, [(dppp)Pt(µ-NMe)] 2 . We have prepared related diimido complexes by deprotonation of diamido complexes, but not with dppp, and only for aryl imido ligands.…”

Section: Discussionmentioning

confidence: 99%

“…We had anticipated that reduction of 1 with Li would result in cleavage of the N−N bond. Reductive cleavage of the Fe analogues of 1 to diimido or diamido complexes by addition of an Fe(CO) 3 fragment or dihydrogen have been reported, as have several other examples of diazo cleavage. ,,,− The lack of success with 1 may be due to the instability of the expected diimido product, [(dppp)Pt(μ-NMe)] 2 . We have prepared related diimido complexes by deprotonation of diamido complexes, but not with dppp, and only for aryl imido ligands. , Future work will be directed to closing this gap between analogues of 1 and diimido complexes by using more suitable ligand systems.…”

Section: Discussionmentioning

confidence: 99%

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Platinum(II) Hydrazido Complexes

Xia

Sharp

2001

Inorg. Chem.

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Reaction of 1,2-dimethylhydrazine with the platinum hydroxo complex [(dppp)Pt(mu-OH)](2)(BF(4))(2) gives the bridging 1,2-dimethylhydrazido(-2) product [(dppp)(2)Pt(2)(mu-eta(2):eta(2)-MeNNMe)](BF(4))(2) 1. Crystals of 1.CH(2)Cl(2) from CH(2)Cl(2)/Et(2)O are monoclinic (C/2) with a = 19.690(1), b = 18.886(1), c = 17.170 (1) A, and beta = 92.111(1) degrees. Treatment of [(dppp)Pt(mu-OH)](2)(OTf)(2) with 1,1-dimethylhydrazine gives [(dppp)(2)Pt(2)(mu-OH)(mu-NHNMe(2))](OTf)(2) 2. Crystals of 2.CH(2)Cl(2) from CH(2)Cl(2)/Et(2)O are triclinic (P-1) with a = 12.910 (3), b = 13.927(3), c = 17.5872 (3) A, alpha = 87.121(3), beta = 89.997(4), and gamma = 84.728(3) degrees. Reaction of [(dppp)Pt(mu-OH)](2)(OTf)(2) with 1 equiv of phenylhydrazine in CH(2)Cl(2) gives [(dppp)(2)Pt(2)(mu-OH)(mu-NHNHPh)](OTf)(2) 3. Two equivalents of phenylhydrazine with [(dppp)Pt(mu-OH)](2)(X)(2) gives [(dppp)Pt(mu-NHNHPh)](2)(X)(2) 4 (X = BF(4), OTf). Crystals of 3.ClCH(2)CH(2)Cl from ClCH(2)CH(2)Cl/(i)()Pr(2)O are monoclinic (P2(1)/n) with a = 20.990(2), b = 13.098(1), c = 25.773 (2) A, and beta = 112.944(2) degrees. Crystals of 4(X = BF(4)).ClCH(2)CH(2)Cl(.)()2((t)()BuOMe) from ClCH(2)CH(2)Cl/(t)()BuOMe are monoclinic (C2/m) with a = 30.508(1), b = 15.203(1), c = 19.049 (1) A, and beta = 118.505(2) degrees.

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Section: Discussionmentioning

confidence: 89%

“…Closely related [(dppm-H)Pt(μ-NHNH 2 )] 2 LiBF 4 also shows this bonding mode, but with a Li−N interaction with the free end of the hydrazido ligands − …”

Section: Discussionmentioning

confidence: 96%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Platinum(II) Hydrazido Complexes

Xia

Sharp

2001

Inorg. Chem.

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Synthesis, Structural Characterization, Solvatochromism, and Electrochemistry of Tetra-Osmium Carbonyl Clusters Containing Azo-Ligands

Lin

Wong

2001

Eur. J. Inorg. Chem.

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The reaction of [Os4(μ‐H)4(CO)12] with 4‐(2‐pyridylazo)‐N,N‐dimethylaniline (PNNDA) in dichloromethane afforded the new clusters [Os4(μ‐H)4(CO)11{NC5H4(N=N)C6H4NMe2}] (1) and [Os4(μ‐H)4(CO)10{η2‐NC5H4(N=N)C6H4NMe2}] (2) in 34% and 15% yields, respectively. Upon heating in toluene under reflux, compound 1 converted into 2 in 80% yield. The MLCT transition of compound 2 shows strong solvent dependency, displaying unusually large positive solvatochromism in different organic solvents. Treatment of [Os4(μ‐H)4(CO)12] with 2‐(5‐bromo‐2‐pyridylazo)‐5‐(diethylamino)phenol (Br‐PADAP) in dichloromethane gives [Os4(μ‐H)3(CO)10{μ‐η3‐Et2NC6H3(O)(N=N)C5NH3Br}] (3). The O−H bond activation is observed and the azo‐ligand behaves as a five‐electron donor. The clusters [Os4(μ‐H)2(CO)10{μ‐η3‐NC5H4(N=N)C5H4N}] (4) and [Os4(μ‐H)4(CO)10{μ‐η2‐NC5H4(N=N)C5H4N}]2 (5) were isolated from the reaction of [Os4(μ‐H)4(CO)10(NCMe)2] with 2,2′‐azopyridine and 3,3′‐azopyridine, respectively. In compound 4, both pyridine and azo nitrogen atoms were found to coordinate to the cluster core. Dehydrogenation was also observed in this compound. For compound 5, two tetra‐osmium metal cores were connected by two azo ligands through their pyridyl nitrogen atoms to form a novel cyclic structure. The redox properties of the compounds described herein were investigated by means of cyclic voltammetry and controlled potential coulometry. Both compound 2 and 5 exhibit a reversible cathodic wave, which indicates that they undergo addition of one electron without significant structural changes. Furthermore, compound 5 displays an electronic interaction between two redox centers, the extra electrons are believed to delocalize throughout the cyclic structure.

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Azoalkan‐ und Nitren‐verbrückte Carbonylmetall‐Cluster des Eisens und Rutheniums

1991

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Azoalkane-and Nitrene-Bridged Carbonyl Metal Clusters of Iron and RutheniumBy using cluster buildup reactions, the new azoalkane-bridged cluding the new compound Fe,(C0)11(b4-NEt)2 (9). Cluster clusters Ru3(CO),(RN=NR) (3a, R = Me, 3b, R = Et), buildup starting from Ru3(C0)9(p3-NPh)2 resulted in Fe2Ru(CO),(EtN =NEt) (4), RU~(CO)~~(RN=NR) (5a, R = Me, R U~( C O )~~(~~-N P~) , (10) and F~R u~( C O )~~(~~-N P~)~ (11). The 5b, R = Et), and FeRu3(CO)12(EtN=NEt) (6) were obtained. crystal structures of 5b and 9 as well as some reactions of the Upon attempts to prepare further such compounds, the N -N nitrene-bridged clusters are described. bond was cleaved resulting in nitrene-bridged clusters inDie Chemie Azoalkan-verbriickter Cluster ist am Beispiel carbocyclischer Azoverbindungen schon recht friih von Kisch') entwickelt worden. Entsprechende Versuche zur Gewinnung Azoaren-verbruckter Systeme, nach anfanglichen Arbeiten von Pauson') vorwiegend von Bruce3) und Gladfelter4) betrieben, haben bis jetzt unter Spaltung der N -N-Bindung stets zu aromatischen Nitrenderivaten gefuhrt. Unsere Beitrage zu dieser Thematik gingen aus von der isoelektronischen Beziehung zwischen den Clustern FeCo2(C0)9(RC = CR) und Fe3(C0)9(RN = NR) und fiihrten zur Beobachtung der intramolekularen N -N-Spaltung gema13 l + 2') sowie zu einigen organischen Synthesen uber solche Cluster6). Wir waren jetzt bemiiht, das darin liegende Reaktionspotential auf andere Metalle und andere Azoverbindungen auszudehnen. Die vorliegende Arbeit, von der ein Ergebnis schon kurz mitgeteilt wurde'), beschreibt unsere diesbezuglichen Versuche mit Eisen-und Rutheniumclustern. EtWeise entstand auch das Azomethan-Derivat 3a, das aber noch reaktiver ist als 3b und deshalb nicht rein isoliert wer- Aus den Umsetzungen zur Bildung von 3a konnte dieses nicht analysenrein gewonnen werden. Zusammen mit 3a fiel aber kristallin und rein ein hoherkerniges Produkt an, das nach der Identifizierung von 5b (s. u.) als 5a erkannt wurde.Auch bei der Aufbaureaktion zu 4 fiel in kleiner Ausbeute ein analoges Nebenprodukt an, das erst durch die Strukturanalyse (s. u.) als 5b identifiziert wurde. Das gleiche Ne-

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Carbon-hydrogen cleavage versus nitrogen-nitrogen cleavage in .mu.3-.eta.2 azoalkane ligands on the M3(CO)9 clusters of iron, ruthenium, and osmium

Cited by 19 publications

References 0 publications

Platinum(II) Hydrazido Complexes

Platinum(II) Hydrazido Complexes

Synthesis, Structural Characterization, Solvatochromism, and Electrochemistry of Tetra-Osmium Carbonyl Clusters Containing Azo-Ligands

Azoalkan‐ und Nitren‐verbrückte Carbonylmetall‐Cluster des Eisens und Rutheniums

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