Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

Widemann, Max; Eichele, Klaus; Schubert, Hartmut; Sindlinger, Christian P.; Klenner, Steffen; Pöttgen, Rainer; Wesemann, Lars

doi:10.1002/ange.202015725

Cited by 9 publications

(2 citation statements)

References 105 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…One very recent report on unique binding modes in ferrato‐stannylene systems featuring the [Cp*( i Pr 2 MeP)Fe] (Cp*=η 5 ‐[C 5 Me 5 ] − ) anionic fragment have been reported by Tilley et al., [17] whilst a Rh −I metallo‐stannylene recently reported by Wesemann et al. was shown to activate H 2 in the formation of a Rh I metallo‐stannylene, [18] though a mechanistic investigation into the involvement of the Sn II center was not disclosed.…”

Section: Introductionmentioning

confidence: 99%

Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**

et al. 2023

View full text Add to dashboard Cite

The open‐shell cationic stannylene‐iron(0) complex 4 (4=[PhiPDippSn⋅Fe⋅IPr]+; PhiPDipp={[Ph2PCH2Si(iPr)2](Dipp)N}; Dipp=2,6‐iPr2C6H3; IPr=[(Dipp)NC(H)]2C:) cooperatively and reversibly cleaves dihydrogen at the Sn−Fe interface under mild conditions (1.5 bar, 298 K), in forming bridging hydrido‐complex 6. The One‐electron oreduction of the related GeII−Fe0 complex 3 leads to oxidative addition of one C−P linkage of the PhiPDipp ligand in an intermediary Fe−I complex, leading to FeI phosphide species 7. One‐electron reduction reaction of 4 gives access to the iron(−I) ferrato‐stannylene, 8, giving evidence for the transient formation of such a species in the reduction of 3. The covalently bound tin(II)‐iron(−I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe−I in this unique d9‐iron complex.

show abstract

Section: Introductionmentioning

confidence: 99%

Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**

et al. 2023

View full text Add to dashboard Cite

show abstract

“…In the past few years there has been growing interest in using heterometallic complexes for H2 activation. Transition metal complexes supported by Lewis-acidic B, [1][2][3] Mg, 4,5 Al, 6 Zn, 7,8 and Sn 9,10 ligands have all been documented to react with H2 under thermal conditions. Despite the rapid growth of this area, examples of photolytic H2 splitting using these types of heterometallic complexes are rare.…”

Section: Introductionmentioning

confidence: 99%

Photochemical H2 Activation by an Zn–Fe Heterometallic: A Mechanistic Investigation

Perez-Jimenez,

Crimmin

2023

Preprint

View full text Add to dashboard Cite

Addition of H2 to a Zn–Fe heterometallic complex was observed to occur under photochemical conditions (390 or 428 nm LED) and leads to the formation of the corresponding metal dihydride. The reaction does not occur under thermal conditions and DFT calculations suggest this is an endergonic, light driven process. Through a combined experimental and computational approach, the plausible mechanisms for H2 activation were investigated. Inhibition experiments, double-label cross-over experiments, radical trapping experiments, EPR spectroscopy and DFT calculations were used to gain insight into this system. The combined data are consistent with two plausible mechanisms, the first involving ligand dissociation followed by oxidative addition of H2 at the Fe centre, the second involving homolytic fragmentation of the Zn–Fe heterometallic and formation of radical intermediates.

show abstract

The Heaviest Bottleable Metallylone: Synthesis of a Monatomic, Zero‐Valent Lead Complex (“Plumbylone”)

Pan

Yao

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

The elusive plumbylone {[Si II (Xant)Si II ]Pb 0 } 3 stabilized by the bis(silylene)xanthene chelating ligand 1,[Si II (Xant)Si II =PhC(NtBu) 2 Si(Xant)Si(NtBu) 2 CPh], and its isolable carbonyl iron complex {[Si II -(Xant)Si II ]Pb 0 Fe(CO) 4 } 4 are reported. The compounds 3 and 4 were obtained stepwise via reduction of the lead(II) dibromide complex {[Si II (Xant)Si II ]PbBr 2 } 2, prepared from the bis(silylene)xanthene 1 and PbBr 2 , employing potassium naphthalenide and K 2 Fe(CO) 4 , respectively. While the genuine plumbylone 3 is rather labile even at À 60 °C, its Pb 0 !Fe(CO) 4 complex 4 turned out to be relatively stable and bottleable. However, solutions of 4 decompose readily to elemental Pb and {[Si II (Xant)Si II ]Fe(CO) 3 } 5 at 80 °C. Reaction of 4 with [Rh(CO) 2 Cl] 2 leads to the formation of the unusual dimeric [(OC) 2 RhPb(Cl)Fe(CO) 4 ] complex 6 with trimetallic RhÀ PbÀ Fe bonds. The molecular and electronic structures of 3 and 4 were established by Density Functional Theory (DFT) calculations.

show abstract

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

Cited by 9 publications

References 105 publications

Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**

Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**

Photochemical H2 Activation by an Zn–Fe Heterometallic: A Mechanistic Investigation

The Heaviest Bottleable Metallylone: Synthesis of a Monatomic, Zero‐Valent Lead Complex (“Plumbylone”)

Contact Info

Product

Resources

About