Synthesis, Coordination, and Catalytic Use of 1'- (Diphenylphosphino)ferrocene-1-sulfonate Anion
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10376030" target="_blank" >RIV/00216208:11310/18:10376030 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1021/acs.organomet.8b00178" target="_blank" >https://doi.org/10.1021/acs.organomet.8b00178</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.organomet.8b00178" target="_blank" >10.1021/acs.organomet.8b00178</a>
Alternative languages
Result language
angličtina
Original language name
Synthesis, Coordination, and Catalytic Use of 1'- (Diphenylphosphino)ferrocene-1-sulfonate Anion
Original language description
Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO(3)H (2; fc = ferrocene-1,1'-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO(3)(HNEt3) (3). Methyl triflate/P(NMe2)(3) can be used to convert compound 3 to the stable sulfonate salt Ph(2)PfcSO(3) (HNEt3) (4) and Ph2P(Me)fcSO(3) (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1'-(diphenylphosphino)-1-bromoferrocene (6; Ph(2)PfcBr) and trapping of the lithiated intermediate with SO3 . NMe3. Reactions of [(L-NC)PdX](2)and [(L-SC)PdX](2), where X = Cl, AcO, L-NC = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1, and L-SC = 2[(methylthio-kappa S)methyl]phenyl-kappa C-1, with 4 uniformly produced the bis-chelate complexes [(L-NC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (7) and [(L-SC)Pd(Ph(2)PfcSO(3)-kappa O-2,P)] (8), respectively. The reaction of [PdCl2(MeCN)(2)] with 4 afforded the bis(phosphine) complex trans-(Et3NH)(2)[PdCl2 (Ph(2)PfcSO(3)-kappa P)(2)] (9). Complexes 7-9 were used as defined catalyst precursors for the Suzuki- Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Organometallics
ISSN
0276-7333
e-ISSN
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Volume of the periodical
37
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
1615-1626
UT code for WoS article
000433635600012
EID of the result in the Scopus database
2-s2.0-85048110168