97688-99-8Relevant academic research and scientific papers
LINEARE OLIGOPHOSPHAALKANE. IX. TERTIAER-SEKUNDAERE METHYLENBISPHOSPHANE; NEUE BRUECKENLIGANDEN UND PHOSPHINIDENQUELLEN IN DER CLUSTERSYNTHESE
Brauer, David J.,Hietkamp, Sibbele,Sommer, Herbert,Stelzer, Othmar
, p. 187 - 204 (1985)
Methylene-bridged tertiary-secondary phosphanes R2PCH2PRH (R = i-Pr, CH2Ph, Me; Ia-Ic) react with excess diironenneacarbonyl to form the violet-coloured clusters Fe3(CO)9(μ2-H)(μ2-PRCH2PR2) (IIIa-IIIc).The crystal structure of the isopropyl derivative shows the Fe3-unit capped by the five-electron donor bridge RP(1)-CH2-P(2)R2 (Fe(1,2)-P(1) 2.1779(8), 2.194(1), Fe(3)-P(2) 2.293(1) Angstroem) while the μ-hydrogen atom is localized between iron atoms Fe(2) and Fe(3).At elevated temperatures, the P-C-P skeleton in IIIa-IIIb is cleaved, leading to PR2CH3-substituted μ3-PR clusters Fe3(CO)9(PR2CH3)(μ3-PR) (IVa, IVb) and subsequently to Fe3(CO)10(μ3-PR) (Va, Vb).With Fe2(CO)9 in a 1/2 molar ratio the phosphanes Ia and Ib under mild pyrolytic conditions form the dihydro clusters Fe3(CO)8(μ2-H)2(PR2CH3)(μ3-PR) (VIa, VIb) in addition to Fe(CO)4(PR2CH3) and the cluster Fe3(CO)9(μ3-PR)2 (VIIa, VIIb).
Linear Oligophosphaalkanes, XII. PH-Functional Methylenebisphosphanes - a Source of Phosphinidenes and Phosphorus Atoms in Clusters and Fe4P Spiro Compounds
Brauer, David J.,Hietkamp, Sibbele,Sommer, Herbert,Stelzer, Othmar
, p. 1677 - 1690 (2007/10/02)
On reacting PH-functional methylenebisphosphanes (iPr)HPCH2PH2 (1) and RHPCH2PR2 (R = CH2Ph) with excess Fe2(CO)9 P - C - P bond cleavage occurs.As a result μ3-phosphido bridged clusters e.g.Fe3(CO)8(μ2-PRCH2PR2)(μ3-PR)(μ2-H) (11) and Fe4(μ4-P) spiro compounds with naked phosphorus atoms Fe4(CO)13(μ4-P)(μ2-PRCH2PR2) (10) or Fe4(CO)14(μ4-P)(μ2-P(iPr)Me) (6) are obtained.Uptake of one molecule of CO by 11 and α-metallation of one CH2Ph substituent within the PR2 donor group yields 12.Compound 10*CH2Cl2 crystallizes in the space group C2/c with a = 36.357(7), b = 10.752(2), c = 22.879(5) Angstroem, β = 112.45(1) deg, Z = 8 (R = 0.050 for 5213 reflections).Both the phosphido atoms of the μ2-PRCH2PR2 group and the μ4-P atom span the Fe 1 - Fe 2 bond of a Fe2(CO)6 species while only the μ4-P atom spans the Fe 3 - Fe 4 bond of a (CO)4FeFe(CO)3 fragment.In addition, the Fe(CO)3 part of the latter unit is bonded to the tertiary P atom of the μ2-PRCH2PR2 group.Compounds 11 and 12 cocrystallize in the space group P with a = 11.541(2), b = 17.739(2), c = 19.284(2) Angstroem, α = 78.01(1), β = 78.68(1), γ = 90.36(1) deg, Z = 2 of each (R = 0.051 for 10234 reflections).A (CO)3Fe - Fe(CO)2 - Fe(CO)3 core having an acute Fe 11 - Fe 12 - Fe 13 angle of 77.46(3) deg at the Fe(CO)2 group is found for 11.The Fe 12 - Fe 13 bond is bridged by both the μ3-PR group and the hydride ligand.The Fe 11 - Fe 13 contact is spanned by the μ3-PR ligand and the μ2-P atom of the μ2-PRCH2PR2 species.Three Fe(CO)3 groups are bridged by the μ3-PR ligand in 12.Only two of the Fe(CO)3 groups appear to be directly bonded.Fe 21 - Fe 23 is bridged by the μ2-P atom of the μ2-PRCH2PRCHPh ligand while Fe 22 - Fe 23 displays a novel Fe 22 - P - C - Fe 23 linkage. - Key words: PH-Functional Methylenebisphosphanes, Phosphinidene Fragmentation, Linear Oligophosphaalkanes, Benzyl Derivatives, α-Metallation
