(R2PC2H4PR2)Pd0-1-Alkyne Complexes
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- 作者：Frank Schager ; Werner Bonrath ; Klaus-Richard Pö ; rschke ; Magnus Kessler ; Carl Krü ; ger ; and Klaus Seevogel
- 刊名：Organometallics
- 出版年：1997
- 出版时间：September 30, 1997
- 年：1997
- 卷：16
- 期：20
- 页码：4276 - 4286
- 全文大小：485K
- 年卷期：v.16,no.20(September 30, 1997)
- ISSN：1520-6041
文摘
Displacement of the ethene ligand in(dippe)Pd(C2H4)(dippe =iPr2PC2H4PiPr2)by 1-alkynesRC
CH affords the mononuclear complexes(dippe)Pd(RCCH) (R = Me(2a), Ph (3a), CO2Me (4), SiMe3 (5)). The molecularstructure of 3a has been determined by X-raycrystallography. Mononuclear 2a and 3a have beenreacted with stoichiometric amounts of(dippe)Pd(
1-C3H5)2as a source for [(dippe)Pd0] toyield the dinuclear derivatives{(dippe)Pd}2(
-RCCH) (R = Me (2b), Ph(3b)). By the reaction of(dippe)Pd(C2H4) withdifunctionalvinylacetylene the mononuclear complex(dippe)Pd{(1,2-2)-RCCH}(R = CH=CH2 (6a)) isformed, which is in equilibrium with isomeric(dippe)Pd{(3,4-2)-H2C=CHCCH}(6b).Addition of [(dippe)Pd0] to6a,b yields dinuclear{(dippe)Pd}2(-RCCH) (R= CH=CH2 (6c)).Reaction of(dippe)Pd(C2H4) withbutadiyne affords(dippe)Pd(2-HCCCCH)(7c). Fromdippe, Pt(cod)2, andC4H2 the Pt homologue has also been synthesizedand thus, togetherwith the already known Ni derivative, the series(dippe)M(2-HCCCCH) (M = Ni(7a),Pd (7c), Pt (7f)) is now complete. When7c and [(dippe)Pd0] arecombined, the dinuclearcomplex{(dippe)Pd}2(-RCCH) (R= CCH (7e)) is formed in solution, whereasisomeric{(dippe)Pd}2{-(1,2-2):(3,4-2)-HCCCCH}(7d) is present in the solid state. Thepreparation of the Pd0-1-alkyne complexes refutes theconventional wisdom that this type ofcompound is inherently unstable. By reaction of(dippe)Pd(C2H4) withinternal alkynes C2R2the complexes (dippe)Pd(RCCR) (R = Me(8a), Ph (9), CO2Me(10), SiMe3 (11)) havealsobeen prepared. Combining 8a with[(dippe)Pd0] affords dinuclear{(dippe)Pd}2(-MeCCMe)(8b). Finally, solution thermolysis of 2band 8b gives rise to dinuclear alkyne-freePd2(dippe)2 (12).
CH affords the mononuclear complexes(dippe)Pd(RCCH) (R = Me(2a), Ph (3a), CO2Me (4), SiMe3 (5)). The molecularstructure of 3a has been determined by X-raycrystallography. Mononuclear 2a and 3a have beenreacted with stoichiometric amounts of(dippe)Pd(1-C3H5)2as a source for [(dippe)Pd0] toyield the dinuclear derivatives{(dippe)Pd}2(-RCCH) (R = Me (2b), Ph(3b)). By the reaction of(dippe)Pd(C2H4) withdifunctionalvinylacetylene the mononuclear complex(dippe)Pd{(1,2-2)-RCCH}(R = CH=CH2 (6a)) isformed, which is in equilibrium with isomeric(dippe)Pd{(3,4-2)-H2C=CHCCH}(6b).Addition of [(dippe)Pd0] to6a,b yields dinuclear{(dippe)Pd}2(-RCCH) (R= CH=CH2 (6c)).Reaction of(dippe)Pd(C2H4) withbutadiyne affords(dippe)Pd(2-HCCCCH)(7c). Fromdippe, Pt(cod)2, andC4H2 the Pt homologue has also been synthesizedand thus, togetherwith the already known Ni derivative, the series(dippe)M(2-HCCCCH) (M = Ni(7a),Pd (7c), Pt (7f)) is now complete. When7c and [(dippe)Pd0] arecombined, the dinuclearcomplex{(dippe)Pd}2(-RCCH) (R= CCH (7e)) is formed in solution, whereasisomeric{(dippe)Pd}2{-(1,2-2):(3,4-2)-HCCCCH}(7d) is present in the solid state. Thepreparation of the Pd0-1-alkyne complexes refutes theconventional wisdom that this type ofcompound is inherently unstable. By reaction of(dippe)Pd(C2H4) withinternal alkynes C2R2the complexes (dippe)Pd(RCCR) (R = Me(8a), Ph (9), CO2Me(10), SiMe3 (11)) havealsobeen prepared. Combining 8a with[(dippe)Pd0] affords dinuclear{(dippe)Pd}2(-MeCCMe)(8b). Finally, solution thermolysis of 2band 8b gives rise to dinuclear alkyne-freePd2(dippe)2 (12).