One-pot synthesis and the X-ray structures of rhenium(I) diphosphine hydrides, fac-(CO)3(P-P)ReH [P-P = dppp, dppb, and dppfe]

Article abstract of DOI:10.1016/j.inoche.2004.10.020

Rhenium(I) tricarbonyl (diphosphine) hydrides have been synthesized in high yield from one-pot reaction of Re₂(CO)₁₀ with diphosphines in refluxed pentanol. The reactions of Re₂(CO) ₁₀ with chelated diphosphines

Full text of DOI:10.1016/j.inoche.2004.10.020

Inorganic Chemistry Communications 8 (2005) 14–17
www.elsevier.com/locate/inoche
One-pot synthesis and the X-ray structures of rhenium(I) diphosphine
hydrides, fac-(CO)3(P–P)ReH [P–P = dppp, dppb, and dppfe]
a
David M. Kimari , Anna M. Duzs-Moore , Jaquay Cook , Kristine E. Miller ,
a
a
b
c
d
Theodore A. Budzichowski , Douglas M. Ho , Santosh K. Mandal
a,
*
a
Department of Chemistry, Morgan State University, 1700 E. Cold Spring Lane, Baltimore, MD 21251, USA
b
Department of Chemistry, Goucher College, Baltimore, MD 21204, USA
c
Department of Chemistry, University of Maryland Baltimore County, Baltimore, MD 21250, USA
d
Department of Chemistry, Princeton University, Princeton, NJ 08544-1009, USA
Received 16 August 2004; accepted 14 October 2004
Available online 24 November 2004
Abstract
The reactions of Re2(CO)10 with chelated diphosphines, P–P, where P–P are 1,3-bis(diphenylphosphino)propane (dppp), 1,4-
bis(diphenylphosphino)butane (dppb), and 1,10-bis(diphenylphosphino)ferrocene (dppfe), in refluxed 1-pentanol or 1-hexanol afford
the corresponding hydrides 1–3 fac-(CO)3(P–P)ReH, (for 1, P–P is dppp, for 2, P–P is dppb, and for 3, P–P is dppfe) in high yield.
The hydrides 1–3 have been characterized spectroscopically and by X-ray crystal structure determinations.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Rhenium; Diphosphines; Hydrides; Crystal structures
Re2ðCOÞ þ 2Na ! 2½ðCOÞ ReꢀNa
ð2Þ
ð3Þ
Rhenium(I) tricarbonyl-diphosphine hydrides, fac-
(CO)3(P–P)ReH, (L–L = diphosphine) are of interest be-
cause they serve as starting materials for the synthesis of
a wide variety of organometallic compounds [1–7]. It is,
therefore, important to find out an easy method of syn-
thesis of rhenium(I) tricarbonyl-diphosphine hydrides,
fac-(CO)3(P–P)ReH. A general method of synthesis of
rhenium(I) tricarbonyl-diphosphine hydrides is to treat
rhenium pentacarbonyl hydride with the corresponding
diphosphines, P–P, as shown in Eq. (1) [8,9]:
10
5
½ðCOÞ ReꢀNa þ H3PO4 ! ðCOÞ ReH þ ½H2PO4ꢀNa
5
5
(CO)5ReH was also prepared from the reaction of
zinc and acetic acid with Re(CO)5Br [12]. The later
was obtained from the reaction of Re2(CO)10 with liquid
bromine [13]. Here, we report a relatively easy one-pot
synthesis and X-ray structures of the rhenium(I) tricar-
bonyl-diphosphine hydrides, fac-(CO)3(dppp)ReH (1),
fac-(CO)3(dppb)ReH (2), and fac-(CO)3(dppfe)ReH
(3), where, dppp is 1,3-bis(diphenylphosphino)propane,
dppb is 1,4-bis(diphenylphosphino)butane, dppfe is
1,10-bis(diphenylphosphino)ferrocene.
Reaction of Re2(CO)10 with diphosphines, P–P in 1-
pentanol produces the hydrides, 1–3 in high yield [14].
Similar reaction of Re2(CO)10 with triphenylphosphine
for several days yielded an unidentified compound,
rather than the expected hydride, cis-(CO)4(PPh3)ReH
ðCOÞ ReH þ P–P ! ðCOÞ ðP–PÞReH þ 2CO
ð1Þ
5
3
However, the synthesis of (CO)5ReH is a long and te-
dious process, involves special glassware or equipment,
requires extensive vacuum-line manipulations, and is a
two-step process as shown in Eqs. (2) and (3) [10,11]:
*
Corresponding author. Tel.: +1 4438851665; fax: +1 4438858286.
E-mail addresses: skmandal2000@yahoo.com, smandal@morgan.
edu (S.K. Mandal).
1387-7003/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2004.10.020

D.M. Kimari et al. / Inorganic Chemistry Communications 8 (2005) 14–17
15
[9]. We did not attempt to identify this unknown com-
pound at this time. Therefore, the present method of
synthesis of the diphosphine hydrides 1–3 cannot be ap-
plied for the synthesis of analogous monophosphine hy-
drides, cis-(CO)4(PPh3)ReH. The diphosphine hydrides,
1–3 have been characterized spectroscopically. The IR
spectrum of each exhibits three strong m(C„O)Õs in the
region 2015–1915 cmꢁ1, characteristic of facial geometry
[9]. Similar m(C„O)Õs were also observed in the IR spec-
trum of fac-(CO)3(dppe)ReH [9]. The H NMR spec-
trum of each shows a very high field resonance as
1
triplet in the region d ꢁ4.0 to ꢁ5.0, due to the hydride
˚
Fig. 1. The X-ray crystal structure of fac-(CO)3(dppp)ReH (1). Selected bond lengths (A): Re(1)AC(1), 1.949(5); Re(1)AC(2), 1.941(4); Re(1)AP(1),
2.4497(9); Re(1)AH(1), 1.70(4). Selected bond angles (ꢁ): O(1)AC(1)ARe(1), 178.4(5); O(2)AC(2)ARe(1), 179.1(3); C(1)ARe(1)AH(1), 171 (2);
C(2)#ARe(1)AP(1), 171.75(11); P(1)ARe(1)AH(1), 78.0(10); C(2)ARe(1)AH(1), 94.1(11); C(3)AP(1)ARe(1), 116.10(11); C(5)AP(1)ARe(1),
116.00(12); C(11)AP(1)ARe(1), 115.31(13).
˚
Fig. 2. The X-ray crystal structure of fac-(CO)3(dppb)ReH (2). Selected bond lengths (A): Re(1)AC(1), 1.948(5); Re(1)AC(2), 1.921(5); Re(1)AC(3),
1.946(5); Re(1)AP(1), 2.4603(12); Re(1)AP(2), 2.4268(11); Re(1)AH(1), 1.75(4). Selected bond angles (ꢁ): O(1)AC(1)ARe(1), 176.1(.4);
O(2)AC(2)ARe(1), 178.9(5); O(3)AC(3)ARe(1), 176.7(4); C(1)ARe(1)AH(1), 173.6(14); C(2)ARe(1)AP(1), 172.0(2); C(3)ARe(1)AP(2), 168.6(2);
P(1)ARe(1)AH(1), 78.7(14); P(2)ARe(1)AH(1), 77.6(14).

16
D.M. Kimari et al. / Inorganic Chemistry Communications 8 (2005) 14–17
˚
Fig. 3. The X-ray crystal structure of fac-(CO)3(dppfe)ReH (3). Selected bond lengths (A): Re(1)AC(1), 1.961(3); Re(1)AC(2), 1.925(4); Re(1)AC(3),
1.942(3); Re(1)AP(1), 2.4466(8); Re(1)AP(2), 2.4723(7); Re(1)AH(1), 1.78(3); Fe(1)ꢂ ꢂ ꢂRe(1), 4.446(1); Fe(1)ꢂ ꢂ ꢂH(1), 4.04(3). Selected bond angles (ꢁ):
O(1)AC(1)ARe(1), 177.8(3); O(2)AC(2)ARe(1), 176.4(3); O(3)AC(3)ARe(1), 175.1(4); C(1)ARe(1)AH(1), 174.7(11); C(2)ARe(1)AP(1), 166.34(10);
C(3)ARe(1)AP(2), 172.31(13); P(1)ARe(1)AH(1), 75.6(11); P(2)ARe(1)AH(1), 86.0(10).
coupled to the two phosphorus atoms. Similar high-field
triplets were observed in related hydrido complexes [9].
The 13C NMR spectrum of each exhibits three low field
resonances in the region d 198–195 as three triplets due
to three terminal COÕs coupled to two phosphorus
atoms. Finally, the three hydrides 1–3 were character-
ized through X-ray crystal structure determinations
[15]. The molecular plots of 1–3 are shown in Figs. 1–
3, respectively. As expected, the central rhenium atom
of each is octahedrally coordinated to three terminal
COÕs in a facial arrangement, two phosphorus atoms
of the chelated diphosphine, P–P, and the hydride li-
gand. Due to the expected low precision of the ReAH
bond distance based on X-irradiation, the observed
ReAH values in 1–3 tabulated below are all the same
within three standard uncertainties, and are comparable
to the value of 1.70(6) observed in mer-Re(CO)3(PPh2O-
Me)H [16]. The displacement of the Re atom off of the
equatorial plane is also comparable to the previous val-
ues observed in other octahedral Re(CO)3(PR3)2H com-
pounds [17]:
deposited with the Cambridge Crystallographic Data
Centre and allocated the deposition numbers CCDC
178949 for compound 1, CCDC 178950 for compound
2, and CCDC 178951 for compound 3. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk)
References
[1] M. Orchin, S.K. Mandal, J. Feldman, Inorg. Synth. 32 (1998)
300.
[2] S.K. Mandal, D.M. Ho, M. Orchin, J. Organomet. Chem. 439
(1992) 53.
[3] S.K. Mandal, J.A. Krause, M. Orchin, J. Organomet. Chem. 467
(1994) 113.
[4] S.K. Mandal, D.M. Ho, M. Orchin, Inorg. Chem. 30 (1991)
2244.
[5] M.T. Williams, C. McEachin, T.M. Becker, D.M. Ho, S.K.
Mandal, J. Organomet. Chem. 599 (2000) 308.
[6] S.K. Mandal, D.M. Ho, M. Orchin, Organometallics 12 (1993)
1714.
˚
Distance (A)
1
2
3
[7] J. Cook, A. Hicks, T. Frazier, D.M. Kimari, T.A. Budzichowski,
J.A. Krause Bauer, S.K. Mandal, J. Chem. Cryst. 33 (2003)
481.
Re–H
Reꢂ ꢂ ꢂ(P2C2)
1.70(4)
0.154(2)
1.75(4)
0.177(2)
1.78(3)
0.165(1)
´ ´
[8] S. Bolan˜o, J. Bravo, R. Carballo, S. Garcıa-Fontan, U. Abram,
´
E.M. Vzquez-Lopez, Polyhedron 18 (1999) 1431.
[9] N. Flitcroft, J.M. Leach, F.J. Hopton, J. Inorg. Nucl. Chem. 32
(1970) 137.
[10] P.S. Braterman, R.W. Harrill, H.D. Kaesz, J. Am. Chem. Soc. 89
(1967) 2851.
Appendix A. Supplementary material
[11] W. Beck, W. Hieber, G. Braun, Z. Anorg. Allg. Chem. 308 (1961)
23.
[12] M.A. Urbancic, J.R. Shapley, Inorg. Synth. 28 (1990) 165.
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been

D.M. Kimari et al. / Inorganic Chemistry Communications 8 (2005) 14–17
17
[13] S.P. Schmidt, W.C. trogler, F. Basolo, Inorg. Synth. 28 (1990) 162.
[14] Synthesis of 1–3: In a typical experiment a mixture of about 2.5
mmol of Re2(CO)10 and 5.0 mmol of the corresponding P–P were
refluxed in 100 mL of 1-pentanol for about 24 h. The mixture was
allowed to cool to room temperature. At this time most of the
hydride came out of the solution. The solid hydride was separated
by filtration and kept aside. The filtrate was evaporated to dryness
using a vacuum pump. The residue was dissolved in 50 ml of
toluene. The toluene solution was passed through a silica gel
column and evaporated to dryness. The residue and the solid
hydride were combined together. The mixture was recrystallized
from CH2Cl2–hexane at ꢁ5 ꢁC. White crystals of 1 and 2 and
orange crystals of 3 were collected by filtration. Data for 1: Yield,
91–93%. M.p. 209–210 ꢁC (dec.). This hydride was characterized
previously [13]. Data for 2: Yield, 81–85%. M.p. 225–228 ꢁC.
Anal. Calc. for C31H29O3P2Re: C, 53.3; H, 4.1. Found: C, 53.0; H,
4.1%. IR (Toluene, cmꢁ1): m(C„O) 2011s, 1930s, 1916s. 1H NMR
(CD2Cl2, d, ppm): 7.55(m, 20H, C6H5), 2.26(m, 4H,
CH2CH2CH2CH2), ꢁ4.61(t, J(PH) 25 Hz, H). 31P (CD2Cl2,
reference: 85% H3PO4, d, ppm): 7.44(s). 13C NMR (CD2Cl2, d,
ppm): 196.54(t, J (PC) 7 Hz, C„O), 195.83(t, J (PC) 19 Hz,
C„O), 195.34(t, J (PC) 19 Hz, C„O), 139.25–128.75(m, C6H5),
32.79(t, J (PC) 14 Hz, APCH2A), 23.88(s, PCH2CH2A). Data for
3: Yield, 89–93%. M.p. 240– 244 ꢁC (dec.). Anal. Calc. for
[15] X-ray intensity data were collected on a Nonius Kappa CCD
diffractometer and corrected for Lorentz-polarization and absorp-
tion effects. The structures were solved by direct methods and
refined by full-matrix least-squares on F2 using SHELXTL (version
5.04). The non-hydrogen atoms were refined anisotropically. The
hydrido ligand H(1) was located in a difference-Fourier map and its
coordinates and isotropic displacement coefficient were also refined.
The remaining H atoms were assigned isotropic displacement
coefficients U(H) = 1.2U(C) and allowed to ride on their respective
carbons. A dichloromethane solvent molecule was also located in
both 1 and 3. Crystal data for 1: C31H29Cl2O3P2Re, M = 768.62,
colorless prisms, 0.29 · 0.20 · 0.12 mm3, orthorhombic, space
˚
˚
group Pnma (No. 62), a = 17.9160(5) A, b = 21.6983(5) A,
c = 7.8031(2) A, V = 3033.43(13) A 3, Z = 4, l(Mo Ka) = 4.318
mmꢁ1, scan mode (x) = 0.5ꢁ · 800, h range = 1.88–27.49ꢁ, 20874
reflections collected, 2968 (I >2rI) unique reflections were used in all
˚
˚
calculations, number of variables = 215, R = 0.0275 (0.0600), Rw
0.0397 (0.0642), and goodness of fit = 1.043. Crystal data for 2:
31H29O3P2Re, M = 697.71, colorless prisms, 0.11 · 0.10 · 0.10
=
C
3
ꢀ
˚
˚
mm , triclinic, space group P1 a = 15.9486(3) A, b = 16.4544(3) A,
3
˚
˚
c = 11.0249(4) A, V = 1514.62(5) A , Z = 2, l(Mo Ka) = 4.522
mmꢁ1, scan mode (x) = 0.5ꢁ · 720, h range = 1.92–27.49ꢁ, 38874
reflections collected, 4689 (I >2rI) unique reflections were used in all
calculations, number of variables = 338, R = 0.0339 (0.0722), Rw
0.0565 (0.0820), and goodness of fit = 1.097. Crystal data for 3:
38H31Cl2FeO3P2Re, M = 910.56, yellow plates, 0.10 · 0.18 · 0.18
=
C
37H29O3P2Re: C, 53.8; H, 3.6. Found: C, 53.6; H, 3.7%. IR
(Toluene, cmꢁ1): m(C„O) 2012s, 1931s, 1921s. 1H NMR (CD2Cl2,
d, ppm): 7.75(m, 20H, C6H5), 4.43(s, br, 1H, C5H4), 4.31(s, br, 1H,
C5H4), 4.25(s, br, 1H, C5H4), 4.13(s, br, 1H, C5H4), ꢁ4.07(t,
J (PH) 28 Hz, H). 31P (CD2Cl2, reference: 85% H3PO4, d, ppm):
14.50(s). 13C NMR (CD2Cl2, d, ppm): 197.04(t, J (PC) 7 Hz,
C„O), 195.98(t, J (PC) 19 Hz, C@O), 195.44(t, J (PC) 21 Hz,
C
3
ꢀ
˚
˚
mm , space group P1 a = 10.0309(4) A, b = 11.0249(4) A, c =
˚
17.8374(8) A, a = 82.945(2)ꢁ,b = 75.587(2)ꢁ, c = 84.389(2)ꢁ, V =
1891.44(13) A , Z = 2, l(Mo Ka) = 3.840 mmꢁ1, scan mode
3
˚
(x) = 1.0ꢁ · 500, h range = 1.18–27.51ꢁ, 17184 reflections collected,
7574 (I >2rI) unique reflections were used in all calculations,
number of variables = 401, R = 0.0273 (0.0647), Rw = 0.0331
(0.0666), and goodness of fit = 1.055.
C„O), 138.78/137.47(t,
J
(PC) 27/21 Hz, ipso, C6H5),
134.77/134.35(t, J (PC) 6/5 Hz, o, C6H5), 130.91/130.37(s, p,
C6H5), 128.69/128.47(t, J (PC) 5/5 Hz, m, C6H5), 78.83–78.12(m,
C5H4), 77.36(s, br, C5H4), 75.32(s, br, C5H4), 73.36(s, br, C5H4),
73.01(s, br, C5H4).
[16] G. Albertin, S. Antoniutti, S. Garcia-Fontan, R. Carballo, F.J.
Padoan, J. Chem. Soc., Dalton Trans. (1998) 2071.
¨
[17] U. FlOrke, H.-J. Haupt, Zeit. Krist. 202 (1992) 317.