A Z-type PGeP pincer germylene ligand in a T-shaped palladium(0) complex

Cabeza, Javier A.; García‐Álvarez, Pablo; Laglera‐Gándara, Carlos J.; Pérez‐Carreño, Enrique

doi:10.1039/d0cc06614a

Cited by 23 publications

(24 citation statements)

References 27 publications

(22 reference statements)

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“…Pale brown and yellow-orange solids were isolated in good yields from the reactions of germylene E with FeCl 2 and CoCl 2 , respectively (Scheme 1). Their microanalytical and mass spectral data, in addition to the previously known tendency of germylenes to get their Ge atom inserted into MÀCl bonds, [11][12][13]17] were consistent with the formula [MCl{k 3 P,Ge,P-GeCl(pyrm-PiPr 2 ) 2 CMe 2 }],M = Fe (1), Co (2). Compounds 1 and 2 are the first PGeP pinceriron and cobaltcomplexes to be reported.…”

Section: Iron(ii)and Cobalt(ii) Complexessupporting

confidence: 71%

“…[12] To improve this situation we have recently synthesized germylene E (Figure 1), [13] which is based on the dipyrromethane scaffold,a nd we have already proven that it forms stable d 10 metal derivatives. [13,17] Although two additional metal-free PGeP germylenes have been recently communicated (D and F in Figure 1), germylene D has only been used as al igand in nickel(0) complexes, [14] and no reaction with aT Mc omplex has yet been reported for germylene F. [18] We now report the reactivity of germylene E with the lightest metal dichlorides of groups 8-12 of the periodic table (Fe-Zn). These reactions have afforded stable chloridogermyl PGeP pincer complexes of earth-abundant metalsw hose metal atoms are in unstrained square planar (Fe II ,C o II ,N i II )o rt etrahedral (Cu I ,Z n II )l igand environments.…”

Section: Introductionmentioning

confidence: 79%

“…Looking for a more flexible ligand framework, we set out the synthesis of germylene C (Figure 1), but the little steric protection of its Ge atom resulted in low stability of the TM derivatives that were prepared [12] . To improve this situation we have recently synthesized germylene E (Figure 1), [13] which is based on the dipyrromethane scaffold, and we have already proven that it forms stable d 10 metal derivatives [13, 17] . Although two additional metal‐free PGeP germylenes have been recently communicated ( D and F in Figure 1), germylene D has only been used as a ligand in nickel(0) complexes, [14] and no reaction with a TM complex has yet been reported for germylene F [18] …”

Section: Introductionmentioning

confidence: 99%

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Reactions of Late First‐Row Transition Metal (Fe‐Zn) Dichlorides with a PGeP Pincer Germylene

Arauzo

Cabeza

Fernández

et al. 2021

Chemistry A European J

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The reactivity of the PGeP germylene 2,2’‐bis(di‐isopropylphosphanylmethyl)‐5,5’‐dimethyldipyrromethane‐1,1’‐diylgermanium(II), Ge(pyrmPiPr2)2CMe2, with late first‐row transition metal (Fe‐Zn) dichlorides has been investigated. All reactions led to PGeP pincer chloridogermyl complexes. The reactions with FeCl2 and CoCl2 afforded paramagnetic square planar complexes of formula [MCl{κ3P,Ge,P‐GeCl(pyrmPiPr2)2CMe2}] (M=Fe, Co). While the iron complex maintained an intermediate spin state (S1; μeff=3.0 μB) over the temperature range 50–380 K, the effective magnetic moment of the cobalt complex varied linearly with temperature from 1.9 μB at 10 K to 3.6 μB at 380 K, indicating a spin crossover behavior that involves S1/2 (predominant at T<180 K) and S3/2 (predominant at T>200 K) species. Both cobalt(II) species were detected by electron paramagnetic resonance at T<20 K. The reaction of Ge(pyrmPiPr2)2CMe2 with [NiCl2(dme)] (dme=dimethoxyethane) gave a square planar nickel(II) complex, [NiCl{κ3P,Ge,P‐GeCl(pyrmPiPr2)2CMe2}], whereas the reaction with CuCl2 involved a redox process that rendered a mixture of the germanium(IV) compound GeCl2(pyrmPiPr2)2CMe2 and a binuclear copper(I) complex, [Cu2{μ‐κ3P,Ge,P‐GeCl(pyrmPiPr2)2CMe2}2], whose metal atoms are in tetrahedral environments. The reaction of the germylene with ZnCl2 led to the tetrahedral derivative [ZnCl{κ3P,Ge,P‐GeCl(pyrmPiPr2)2CMe2}].

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Section: Iron(ii)and Cobalt(ii) Complexessupporting

confidence: 71%

Section: Introductionmentioning

confidence: 79%

Section: Introductionmentioning

confidence: 99%

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Reactions of Late First‐Row Transition Metal (Fe‐Zn) Dichlorides with a PGeP Pincer Germylene

Arauzo

Cabeza

Fernández

et al. 2021

Chemistry A European J

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“…The recent availability of metal-free PGeP germylenes (Figure 1) [1][2][3][4][5][6][7][8] has allowed an advance of the coordination chemistry of PGeP pincer complexes. [1] In fact, some of these germylenes have already led to transition metal (TM) complexes containing either PGeP pincer germylene ligands (just by simple coordination) [7,8] or PGeP pincer germyl ligands (by insertion of the Ge atom into an MÀ Cl bond of the metal precursor).…”

Section: Introductionmentioning

confidence: 99%

Dipyrromethane‐Based PGeP Pincer Methylgermyl and Methoxidogermyl Nickel and Palladium Complexes

et al. 2021

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Dedicated to the memory of Prof. Víctor Riera, a pioneer of the Spanish Organometallic Chemistry, a great teacher and a great mentor.The dipyrromethane-based chloridogermyl complexes [MCl {k 3 P,Ge,P-GeCl(pyrmP i Pr 2 ) 2 CMe 2 }] (1 M ; M = Ni, Pd; (pyrm-P i Pr 2 ) 2 CMe 2 = 5,5'-dimethyl-2,2'-bis(di-isopropylphosphanylmethyl)dipyrromethane-1,1'-diyl) reacted with one or more equivalents of LiOMe to give the monosubstituted complexes [MCl {k 3 P,Ge,P-Ge(OMe)(pyrmP i Pr 2 ) 2 CMe 2 }] (2 MÀ OMe ; M = Ni, Pd). However, analogous treatments of complexes 1 M with LiMe afforded the dimethyl complexes [MMe{k 3 P,Ge,P-GeMe(pyrmP i Pr 2 ) 2 CMe 2 }] (3 MÀ Me ; M = Ni, Pd). The monomethyl complexes [MCl{k 3 P,Ge,P-GeMe(pyrmP i Pr 2 ) 2 CMe 2 }] (2 MÀ Me ; M = Ni, Pd), which were identified as intermediates in the syntheses of 3 MÀ Me , were satisfactorily prepared by treating 3 MÀ Me with HCl. The regioselectivities of these reactions have been rationalized with DFT calculations.

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“…[4][5][6][7][8][9][10][11][12] Moreover, they represent the prospects of new avenues for transition metal/P-element cooperation. [13][14][15][16][17][18][19][20][21][22][23][24][25] However, the coordination chemistry of tetrylenes remains considerably less explored than their lighter carbene congeners, in no little part due to reduced stability. To overcome this limitation base-stabilized tetrylenes have been explored and their complexes have found relevance in catalysis.…”

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confidence: 99%

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

Bajo¹,

Alcaide²,

López-Serrano³

et al. 2021

Preprint

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Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

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A Z-type PGeP pincer germylene ligand in a T-shaped palladium(0) complex

Abstract: A dipyrromethane-based germylene decorated with two phosphane groups has been used to prepare an unusual T-shaped palladium(0) containing a PGeP pincer germylene that acts as a Z-type ligand. This compound...

Cited by 23 publications

References 27 publications

Reactions of Late First‐Row Transition Metal (Fe‐Zn) Dichlorides with a PGeP Pincer Germylene

Reactions of Late First‐Row Transition Metal (Fe‐Zn) Dichlorides with a PGeP Pincer Germylene

Dipyrromethane‐Based PGeP Pincer Methylgermyl and Methoxidogermyl Nickel and Palladium Complexes

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

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