of 11
Supporting information for: Spin-State Effects on the
Thermal Dihydrogen Release from Solid-State
[MH(
η
2
-
H
2
)dppe
2
]
+
(M = Fe, Ru, Os) Organometallic
Complexes for Hydrogen Storage Applications
David G. Abrecht, Jorge A. Muñoz, Hillary L. Smith, and Brent Fultz
W.M. Keck Laboratory, California Institute of Technology, 1200 E. California Blvd, MC 138-78,
Pasadena, CA 91125
E-mail: btf@caltech.edu
To whom correspondence should be addressed
S1
Contents
Figure S.1 Mass Spectrograph of Initial Degassing of [FeH(
η
2
-H
2
)dppe
2
][NTf
2
] . . . S3
Figure S.2 Mass Spectrograph of Hydrogen Cycling onto [FeH(
η
2
-H
2
)dppe
2
][NTf
2
] . S4
Figure S.3 Relaxed structure of singlet [FeHdppe
2
]
+
. . . . . . . . . . . . . . . . . . S5
Figure S.4 Relaxed Structure of Triplet [FeHdppe
2
]
+
. . . . . . . . . . . . . . . . . . S6
Figure S.5 Relaxed Structure of [FeH(
η
2
-H
2
)dppe
2
]
+
. . . . . . . . . . . . . . . . . . S7
Table 1
Calculated Energies of Molecular Fragments . . . . . . . . . . . . . . . . . S8
Table 2
SCS-MP2 Calculated Energies of Molecular Fragments . . . . . . . . . . . S10
S2
0
1.0e-6
2.0e-6
3.0e-6
4.0e-6
5.0e-6
6.0e-6
7.0e-6
8.0e-6
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
Pressure, torr
Mass number, Z/e
-
2.0
14.0
28.0
Figure S.1: Residual mass spectrograph of the initial degassing of as-synthesized [FeH(
η
2
-
H
2
)dppe
2
][NTf
2
] containing N
2
contamination at the binding site. Degassing occurred from the
solid state under vacuum conditions at 393K, and shows the preferential loss of N
2
gas from the
species.
S3
0
1.0e-5
2.0e-5
3.0e-5
4.0e-5
5.0e-5
6.0e-5
7.0e-5
8.0e-5
9.0e-5
1.0e-4
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
Pressure, torr
Mass number, Z/e
-
1
st
cycle
2
nd
cycle
3
rd
cycle
Final cycle
Figure S.2: Residual mass spectrograph of the volatile thermal decomposition products of
[FeH(
η
2
-H
2
)dppe
2
][NTf
2
] during hydrogen cycling at 413 K. Hydrogen gas is the only observed
decomposition product from the material after for all four hydrogenation/dehydrogenation cycles.
S4
Figure S.3: Optimized structure of the singlet state organometallic fragment [FeHdppe
2
]
+
using
the UHF approximation and LANL2DZ-ECP basis sets, showing typical octahedral geometry.
Alkyl and aryl hydrogens have been omitted for clarity.
S5
Figure S.4: Optimized structure of the triplet state organometallic [FeHdppe
2
]
+
using the UHF ap-
proximation and LANL2DZ-ECP basis sets. Structure shows the quasi-square pyramidal structure
observed by Franke,
1
et al. Alkyl and aryl hydrogens have been omitted for clarity.
S6
Figure S.5: Optimized structure of [FeH(
η
2
-H
2
)dppe
2
]
+
using the UHF approximation and
LANL2DZ-ECP basis sets, showing the octahedral geometry observed from x-ray diffraction mea-
surements.
2
Alkyl and aryl hydrogens have been omitted for clarity.
S7