Darstellung, Eigenschaften und Molekülstrukturen von Komplexen des versteiften dreizähnigen Chelatliganden N, N′‐Bis(diphenylphosphino)‐2, 6‐diaminopyridin mit MII‐ und M0‐Übergangsmetallen [MII= Ni, Pd, Pt; M0= Cr, Mo, W]

Schirmer, Wolfgang; Flörke, Ülrich; Haupt, H.‐J.

doi:10.1002/zaac.19875450210

Cited by 93 publications

(69 citation statements)

References 20 publications

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“…Upon treatment of 2 equivalents of iPr 2 PCl with the respective 2,6-diaminopyrimidinein the presence of NEt 3 in THF, these air-stable ligands were isolated in good yields (68-85%) [76] (Scheme 10). 3 in tetrahydrofuran (THF) [63]. Based on the elemental analysis result, mer-[Cr(CO) 3 (L1)]·2THF (Cr1) was obtained.…”

Section: L21mentioning

confidence: 99%

“…Haupt and co-workers prepared [Ni(L1)Cl]Cl (Ni1) by adding the L1 ligand to NiCl 2 ·6H 2 O in ethanol [63]. Analogous bromide complexes were synthesized by the Kirchner group from the PN 3 P ligands and NiBr 2 (DME) (Ni2-Ni4, R= Ph, iPr, and tBu) [68] (Scheme 15).…”

Section: Nickelmentioning

confidence: 99%

“…. These ligands could be prepared in a straightforward fashion starting from 2,6-diaminopyridine or 1,3,5-triazine-2,4-diamine with the respective chlorophosphine compound, R 2 PCl, in the presence of a base, typically NEt 3 and/or n-BuLi [63][64][65][66][67][68][69][70]. The construction of P-N bonds was first reported by Haupt and co-workers and then was further expanded by the Kirchner group.…”

Section: Introductionmentioning

confidence: 99%

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A new class of PN3-pincer ligands for metal–ligand cooperative catalysis

Zheng

Huang

2015

Coordination Chemistry Reviews

174

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Section: L21mentioning

confidence: 99%

Section: Nickelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A new class of PN3-pincer ligands for metal–ligand cooperative catalysis

Zheng

Huang

2015

Coordination Chemistry Reviews

174

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“…They are easily and nearly quantitatively obtainable in two steps from commerciallya vailable and inexpensive startingm aterials.I na ddition, the precatalysts self-activate under basic conditions. [11,15,21] The related pyridine-based PN 3 P pincer ligand class was introduced by Haupt and coworkers [22,23] and has intensively been studied by the Kirchner group.[24]The coupling of 1-phenylethanol (1a)a nd benzyl alcohol (2a)t o3a was chosen as am odel reaction (Table 1, top). Common reactionp arameters were optimized starting with precatalyst 4a (for furtherd etails see the Supporting Information).…”

mentioning

confidence: 99%

Cobalt‐Catalyzed Alkylation of Secondary Alcohols with Primary Alcohols via Borrowing Hydrogen/Hydrogen Autotransfer

Freitag

Irrgang

Kempe

2017

Chemistry A European J

113

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Alcohols are promising sustainable startingm aterials because they can be obtained from abundant and indigestible biomass. The substitution of expensive noble metals in catalysis by earth abundant 3d metals,s uch as Mn, Fe, or Co, (nonprecious or base metals) is ar elated key concept with respect to sustainability. Here, we report on the first cobalt-catalyzed alkylationo fs econdary alcohols with primary alcohols. Easy-to-synthesize and easy-toactivate PN 5 P-pincer-ligand-stabilized Co complexes developed in our laboratory mediate the reaction moste fficiently.T he catalysis is applicable to ab road substrate scope and proceeds under relatively mild conditions. We have even demonstrated the coupling of av ariety of purely aliphatic alcohols with ab ase or nonprecious metal catalyst. Mechanistic studies indicatet hat the reactionf ollows the borrowing hydrogen or hydrogen autotransfer concept.The borrowing hydrogen/hydrogen autotransferm ethodology (BH/HA) is ap rominente xample of an alcohol re-functionalization concept. [1,2] Thea lcohol is dehydrogenated to ac arbonyl compound, followed by ar eaction with an ucleophile and subsequent reduction with the "borrowed" hydrogen. Due to dwindling crude oil reserves and growingp ublica wareness for the consequences of climate change, the search for alternative carbon resources is getting increasingly urgent. [3,4] In this regard, alcohols are promising as startingm aterials due to the possibility of obtaining them from abundantlya vailable, indigestible,a nd barely used biomass (lignocellulose). [5][6][7] The direct hetero-coupling of two alcohols follows the BH/HA concept and exclusively uses alcohols as startingm aterials. This reaction has been reported to proceed employing am ultitude of noble metal catalysts.[8] However,n oble metals are rare and their conservation is ak ey issue with regard to as ustainable future.O ne possible approach is the replacemento fp recious metals in key technologies by more abundant metals. Beside Mn, [9] and Fe, [10] especiallyC oc omplexes have been disclosed as highly active and selectivecatalysts for av ariety of reactions following the BH/HA mechanism (see Scheme 1). [11][12][13][14][15][16][17] Iron- [18] and nickel-based [19] homogenousc atalysts have been described for thea lkylation of secondary alcohols by primary alcohols.[20] Unfortunately,t he substrate scopei sl imited, especially for the nickel-catalyzed version. Ab roadly applicable catalyst system based on an onprecious metal,w hich is capable of coupling aromatic, as well as purely aliphatic alcohols remains unknown.Herein, we report on the first cobalt-catalyzed version of the hetero-alkylation of alcohols by alcohols following the BH/HA concept. The catalyst is able to couple substituted 1-phenylethanol derivatives with primary aromatic or aliphatic alcohols as well as secondary aliphatic alcohols with primary aromatic or aliphatic alcohols. Triazine-based PN 5 Pp incer ligand complexesd eveloped in our laboratory are most efficient in these reactions. ...

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“…[1][2][3] Here, we report on the synthesis and X-ray crystal structure of an open-face ruthenium complex that is a potentially useful starting complex. The three chlorido ligands in the title compound, [RuCl3{N,N¢-bis(diphenylphosphino)-2,6-diaminopyridine}] (1), can thus be replaced by other ligands on demand to produce a wide variety of ruthenium complexes bearing the PNP ligand.…”

mentioning

confidence: 99%